CN109790274B - Urethane resin using polyrotaxane, and polishing pad - Google Patents

Abstract

The present invention provides a urethane resin for a sliding member, which is considered to have a uniform dispersion of crosslinking points, to allow appropriate molecular motion, and to have high wear resistance. In particular, a urethane resin that can be suitably used as a polishing pad is provided. The present invention provides a urethane resin for polishing obtained by polymerizing a polymerizable composition containing: a polyrotaxane (A) having a composite molecular structure formed of an axial molecule and a plurality of cyclic molecules including the axial molecule, wherein a side chain having an active hydrogen-containing group is introduced into at least a part of the cyclic molecules, and a polyiso (thio) cyanate compound (B).

Description

Urethane resin using polyrotaxane, and polishing pad

Technical Field

The present invention relates to a novel urethane resin. More particularly, the present invention relates to a novel urethane resin obtained by polymerizing a specific polymerizable monomer component, and a novel polishing pad containing the urethane resin.

Background

The polishing member is a member used for planarizing a target member to be polished with a polishing agent. Specifically, the polishing member is used for flattening the surface of a member to be polished, while supplying a polishing agent such as slurry to the surface, the polishing agent is brought into sliding contact with the surface. For example, a polishing pad.

Polyurethane resins are often used for such polishing members. In general, as a polishing member, a material having high durability and excellent abrasion resistance for a long period of time is always desired from the viewpoints of cost reduction, stable production, and productivity improvement.

The member for polishing is used specifically as a pad (hereinafter, sometimes referred to as a polishing pad) in a CMP (chemical mechanical polishing) method. The CMP method is a polishing method for imparting excellent surface flatness, and can be used particularly in the production processes of Liquid Crystal Displays (LCDs), glass substrates for hard disks, silicon wafers, and semiconductor devices.

In the CMP method, a polishing method is generally adopted in which a slurry (polishing liquid) obtained by dispersing abrasive grains in an alkaline solution or an acidic solution is supplied to polish the workpiece. That is, the object to be polished is planarized by the mechanical action of the abrasive grains in the slurry and the chemical action of the alkaline solution or the acidic solution. Generally, the surface of the object to be polished is planarized by supplying the slurry to the surface and bringing a polishing pad into contact with the surface while sliding the pad.

As the polishing characteristics of the polishing pad in the CMP method, it is required to impart excellent flatness to an object to be polished and to increase the polishing rate (polishing speed). Further, in order to improve productivity, improvement in wear resistance is desired.

As a material of such a polishing pad, a polishing material obtained from a urethane curable composition containing: the urethane prepolymer contains a main component of a urethane prepolymer obtained by reacting a polyol with a polyisocyanate such as toluene diisocyanate, and a curing agent containing an amine compound (see patent document 1). Further, as a material having further improved abrasion resistance, a polishing material using p-phenylene diisocyanate as a polyisocyanate compound is known (see patent document 2).

However, since the polyol compounds in the polishing materials described in these methods are diol compounds and no crosslinked structure is present in the obtained urethane resin, there is room for improvement in order to meet the recent demand for high wear resistance.

On the other hand, in recent years, the development of polyrotaxane has been proposed as a polymer having a new structure. The polyrotaxane is a functional material having a complex molecular structure formed of an axial molecule and a plurality of cyclic molecules including the axial molecule. As a specific example of development, for example, a polyrotaxane which is used in a worn part and is a member having excellent sliding properties can be cited (for example, see patent document 3).

However, the material containing polyrotaxane described in patent document 3 is considered to be mainly used for sports goods, building materials or medical materials, but there is room for improvement from the viewpoint of satisfying high wear resistance.

In addition, in addition to the above, the following resins were studied using polyrotaxane. For example, a thermoplastic resin containing a polyrotaxane and a thermoplastic polyurethane is known (see patent document 4). The thermoplastic resin described in patent document 4 contains a polyrotaxane, and thus the mechanical properties of the thermoplastic polyurethane resin are improved, but there is room for improvement from the viewpoint of satisfying high abrasion resistance by simply mixing the polyrotaxane and the thermoplastic polyurethane.

In contrast, a method of improving the mechanical properties of polyurethane by incorporating polyrotaxane itself into the molecule of the polyurethane has also been carried out (see patent documents 5 to 7).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2007-77207

Patent document 2: japanese laid-open patent publication No. 2015-178558

Patent document 3: international publication WO2006/115255 pamphlet

Patent document 4: international publication WO2016/114243 pamphlet

Patent document 5: WO2015/159875 pamphlet

Patent document 6: japanese laid-open patent publication No. 2017-48305

Patent document 7: japanese unexamined patent publication No. 2017-75301

Disclosure of Invention

Problems to be solved by the invention

The polyurethanes described in patent documents 5 to 7 can more effectively improve the mechanical properties of the polyurethane.

However, in recent years, development of a high-performance resin has been desired, and particularly, development of a resin having more excellent wear resistance than a conventional urethane resin has been desired for a urethane resin used for a polishing pad. Further, for example, in applications such as a polishing pad, when a semiconductor material such as a wafer is polished, it is desired to stably produce a smooth wafer having a high polishing speed and excellent scratch resistance without causing fine scratches. Therefore, a polishing pad having excellent elastic recovery with low hysteresis is desired in order to have an excellent wear resistance, an appropriate hardness, an excellent abrasion resistance, and a stable polishing at a high polishing rate.

Accordingly, an object of the present invention is to provide a urethane resin for a sliding member having high wear resistance, excellent elastic recovery, and low hysteresis. Particularly, a urethane resin which can be suitably used as a polishing pad is provided.

Means for solving the problems

The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that the above problems can be solved by using, as a member for polishing, a urethane resin obtained by reacting a polyrotaxane having a specific structure, particularly a polyrotaxane having a further modified cyclic molecule, with a polyisocyanate compound, and have completed the present invention.

Namely, according to the present invention, there are provided

(1) A urethane resin obtained by polymerizing a polymerizable composition containing:

a polyrotaxane (A) having a complex molecular structure formed of an axis molecule and a plurality of cyclic molecules including the axis molecule and having an active hydrogen group-containing side chain introduced into at least a part of the cyclic molecules, and

polyiso (thio) cyanate compound (B).

In the present invention, the polyrotaxane (a) is a complex of molecules having the following structure: that is, a chain-like axial molecule penetrates the rings of a plurality of cyclic molecules, and bulky groups are bonded to both ends of the axial molecule, so that the cyclic molecule is not easily pulled out from the axial molecule due to steric hindrance.

Complexes of molecules such as polyrotaxane are called supramolecules (supramolecules).

The following embodiments are suitably employed for the polymerizable composition of the present invention.

(2) The urethane resin according to the item (1), wherein the polymerizable composition contains 3 to 2000 parts by mass of the polyiso (thio) cyanate compound (B) per 100 parts by mass of the polyrotaxane (A).

(3) The polymerizable composition further contains an active hydrogen-containing compound (C) having an active hydrogen-containing group other than the polyrotaxane (A).

(4) The active hydrogen-containing compound (C) contains a Compound (CA) having an amino group as an active hydrogen-containing group.

(5) The polymerizable composition contains, per 100 parts by mass of the polyrotaxane (a):

10 to 3000 parts by mass of the polyiso (thio) cyanate compound (B), and

3 to 2000 parts by mass of the active hydrogen-containing compound (C).

(6) The polyiso (thio) cyanate compound (B) contains:

a urethane prepolymer (B2) having an isocyanate (thio) group at the molecular end, which is obtained by reacting a 2-functional active hydrogen-containing compound (C1) having 2 active hydrogen-containing groups in the molecule with a 2-functional isocyanate (thio) group-containing compound (B1) having 2 isocyanate (thio) groups in the molecule.

(7) The polyisocyanate compound (B) containing the urethane prepolymer (B2) has an isocyanate equivalent weight of 300 to 5000.

(8) A polishing pad comprising the urethane resin according to any one of (1) to (7) above.

Effects of the invention

As shown in examples described later, the urethane resin of the present invention has appropriate hardness, excellent elastic recovery (low hysteresis loss), and high abrasion resistance.

Therefore, when the urethane resin is used as a (polishing material) for a sliding member such as a polishing pad, not only is it excellent in wear resistance, but also it is possible to exert excellent polishing characteristics, i.e., a high polishing rate, low scratching properties, and high flatness.

Drawings

FIG. 1 is an image of polyrotaxane (A) used in the present invention.

Detailed Description

The urethane resin of the present invention is obtained by polymerizing a polymerizable composition containing: a polyrotaxane (A) having a composite molecular structure formed of an axial molecule and a plurality of cyclic molecules including the axial molecule, wherein a side chain having an active hydrogen-containing group is introduced into at least a part of the cyclic molecules, and a polyiso (thio) cyanate compound (B).

The urethane resin of the present invention is a thermosetting urethane resin in which the polyrotaxane (a) is incorporated into the molecule.

First, a description will be given of a polyrotaxane (a) having a complex molecular structure formed of an axial molecule and a plurality of cyclic molecules including the axial molecule and having an active hydrogen group-containing side chain introduced into at least a part of the cyclic molecules (hereinafter, may be simply referred to as "polyrotaxane (a)" or "component (a)").

< Polyrotaxane (A) having a composite molecular structure comprising an axial molecule and a plurality of cyclic molecules including the axial molecule, wherein a side chain having an active hydrogen-containing group is introduced into at least a part of the cyclic molecules

The polyrotaxane (a) used in the present invention has a composite molecular structure represented by "1" as a whole and composed of a chain axis molecule "2", a cyclic molecule "3", and a side chain "5", as shown in fig. 1. That is, a plurality of cyclic molecules "3" include chain axis molecules "2", and the axis molecules "2" pass through the inside of the ring of the cyclic molecules "3". Therefore, the cyclic molecule "3" can freely slide on the axial molecule "2", but bulky terminal groups "4" are formed at both ends of the axial molecule "2" to prevent the cyclic molecule "3" from falling off from the axial molecule "2". Further, a side chain "5" having an active hydrogen-containing group is introduced into the ring of the cyclic molecule "3".

The cyclic molecule "3" of the polyrotaxane (A) can slide on the axial molecule "2". In addition, since a side chain having an active hydrogen-containing group can be introduced from the cyclic molecule "3", the active hydrogen-containing compound (C) described in detail below may be reacted with the polyiso (thio) cyanate compound (B) to form a crosslinked structure or a pseudo-crosslinked structure. As a result, it is presumed that the urethane resin has a crosslinking point which facilitates molecular movement, and the abrasion resistance is improved. Further, it is considered that the urethane resin has a slidable crosslinked structure in its molecule, and therefore has a low hysteresis loss and can exhibit excellent mechanical properties.

The polyrotaxane (A) can be synthesized by a method described in International publication WO2015/068798 pamphlet or the like. The composition of the component (A) will be described.

(Polyrotaxane (A) Axis molecule)

Various axial molecules are known as the polyrotaxane (a). For example, the chain moiety may be linear or branched as long as it can pass through the ring of the cyclic molecule, and is generally formed of a polymer. Specifically, the description is in International publication WO2015/068798 pamphlet or the like.

Suitable polymers forming the chain portion of such an axial molecule include, for example, polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol, and polyvinyl methyl ether, and among these, polyethylene glycol is particularly preferred.

Further, the bulky group formed at both ends of the chain portion is not particularly limited as long as it is a group capable of preventing the cyclic molecule from being detached from the shaft molecule, and from the viewpoint of the bulky group, for example, an adamantyl group, a trityl group, a fluorescein group, a dinitrophenyl group, and a pyrenyl group are exemplified, and among them, from the viewpoint of ease of introduction and the like, an adamantyl group is exemplified.

The molecular weight of the above-mentioned axial molecule is not particularly limited, but when it is too large, the viscosity tends to be high, and when it is too small, the mobility of the cyclic molecule tends to be low. From such a viewpoint, the weight average molecular weight Mw of the axial molecule is preferably 1,000 to 100,000, more preferably 5,000 to 80,000, and particularly preferably 10,000 to 50,000.

(Cyclic molecule of polyrotaxane (A))

The cyclic molecule is a molecule having a ring having a size capable of enclosing the above-described axial molecule, and examples of such a ring include a cyclodextrin ring, a crown ether ring, a benzocrown ether ring, a dibenzocrown ether ring, and a dicyclohexyl crown ether ring, and among these, a cyclodextrin ring is particularly preferable.

The cyclodextrin ring contains alpha-type (ring inner diameter 0.45-0.6 nm), beta-type (ring inner diameter 0.6-0.8 nm), and gamma-type (ring inner diameter 0.8-0.95 nm). In particular, alpha-cyclodextrin rings are most preferred.

The number of cyclic molecules having such a ring as described above is generally in the range of 0.001 to 0.6, more preferably 0.002 to 0.5, and still more preferably 0.003 to 0.4, where the maximum number of clathrates of the cyclic molecules that can be clathrated with respect to 1 axis molecule is 1.

The maximum number of clathrates of a cyclic molecule with respect to 1 axis molecule can be calculated from the length of the axis molecule and the thickness of the ring that the cyclic molecule has. For example, the chain portion of the axial molecule is formed of polyethylene glycol, and the maximum number of inclusion is calculated as follows, taking the case where the ring of the cyclic molecule is an α -cyclodextrin ring as an example.

I.e., the repeating unit [ -CH ] of polyethylene glycol₂-CH₂O-]Approximately 1 alpha-cyclodextrin ring thick. Therefore, the number of repeating units was calculated from the molecular weight of the polyethylene glycol, and 1/2, which is the number of repeating units, was determined as the maximum number of inclusion of cyclic molecules. The maximum inclusion number is set to 1.0, and the inclusion number of the cyclic molecules is adjusted to the above range.

(side chain of cyclic molecule of polyrotaxane (A))

The polyrotaxane (a) used in the present invention is characterized in that a side chain having an active hydrogen-containing group is introduced into the above cyclic molecule. In the present invention, the side chain of the cyclic molecule is a side chain having a certain length. Furthermore, the active hydrogen of the cyclic molecule directly does not correspond to the active hydrogen of the side chain. That is, for example, when the cyclic molecule is an α -cyclodextrin ring, the active hydrogen of the hydroxyl group (OH group) of the α -cyclodextrin ring does not correspond to the active hydrogen of the side chain. In the present invention, it is considered that an excellent effect is exhibited by making a side chain having a certain length have an active hydrogen. As described later, in the present invention, for example, when the cyclic molecule is an α -cyclodextrin ring, it is preferable to react a hydroxyl group (OH group) of the α -cyclodextrin ring with another compound to form a ring having a side chain formed from the other compound, and in this case, it is preferable to introduce active hydrogen into the side chain.

Examples of the active hydrogen-containing group in the side chain include groups selected from the group consisting of a hydroxyl group (OH group), a thiol group (SH group), and an amino group (-NH)₂or-NHR; r is a substituent, such as alkyl). Among them, an OH group is preferable from the viewpoint of good reactivity with the iso (thio) cyanate compound (B).

The side chain having an active hydrogen-containing group is not particularly limited, and is preferably formed by repeating an organic chain having 3 to 20 carbon atoms. The average molecular weight of the side chain is 50 to 10,000, preferably 100 to 8,000, more preferably 200 to 5,000, and most preferably 300 to 1,500. The average molecular weight of the side chain can be adjusted by the amount used for introducing the side chain, and can be obtained by calculation or by calculation¹H-NMR was measured. When the side chain is too short, the uniformity of the surface of the object to be polished tends to be low. On the other hand, when the side chain is too long, the abrasion resistance tends to be lowered.

Such a side chain is introduced by modifying a functional group of a cyclic molecule by using the functional group. For example, α -cyclodextrin rings have 18 OH groups (hydroxyl groups) as functional groups, via which side chains are introduced. That is, up to 18 side chains can be introduced relative to 1 α -cyclodextrin ring. In the present invention, in order to sufficiently exhibit the functions of the side chains, it is preferable that 6% or more, particularly 30% or more of the total number of functional groups of the rings are modified with side chains. The functional group of the cyclic molecule may affect the compatibility with other components, and particularly, when the functional group is an OH group, the functional group has a large effect on the compatibility with other components. Therefore, the ratio (degree of modification) of the modified functional group is preferably 6% to 80%, more preferably 30% to 70%. As described in detail below, the functional group of the cyclic molecule has lower reactivity than the OH group of the side chain, and therefore, even if the degree of modification is low, problems such as reduction in compatibility and bleeding are unlikely to occur. Therefore, the modification degree can exert more excellent effects as long as it is within the above range. When the side chain was bonded to 9 of the 18 OH groups of the above-mentioned α -cyclodextrin ring, the modification degree was 50%.

The side chain (organic chain) may be linear or branched as long as it has an active hydrogen-containing group on the organic chain. In addition, ring-opening polymerization is utilized; free radical polymerization; cationic polymerization; anionic polymerization; living radical polymerization such as atom transfer radical polymerization, RAFT polymerization, NMP polymerization, and the like, and a desired side chain can be introduced by reacting an organic chain (side chain) having an active hydrogen-containing group with the functional group of the above cyclic molecule.

For example, a side chain derived from a cyclic compound such as a lactone or a cyclic ether can be introduced by ring-opening polymerization. The side chain introduced by ring-opening polymerization of a cyclic compound such as a lactone or a cyclic ether may have an OH group as an active hydrogen-containing group introduced at the end of the side chain.

Among the cyclic compounds, cyclic ethers and lactones are preferably used from the viewpoint of easy availability, high reactivity, and easy adjustment of the size (molecular weight). Specific examples of suitable cyclic compounds are described below.

Cyclic ether: ethylene oxide, 1, 2-propylene oxide, epichlorohydrin, bromopropylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, isobutylene oxide, oxetane, 3-methyloxetane, 3-dimethyloxetane, tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, and the like.

Lactone compound:

4-membered ring lactone: for example, beta-propiolactone, beta-methylpropanolide, L-serine-beta-lactone and the like.

5-membered ring lactone: for example, gamma-butyrolactone, gamma-caprolactone, gamma-heptolactone, gamma-octalactone, gamma-decalactone, gamma-dodecalactone, alpha-hexyl-gamma-butyrolactone, alpha-heptyl-gamma-butyrolactone, alpha-hydroxy-gamma-butyrolactone, gamma-methyl-gamma-decalactone, alpha-methylene-gamma-butyrolactone, alpha-dimethyl-gamma-butyrolactone, D-erythroketonolactone, alpha-methyl-gamma-butyrolactone, gamma-nonalactone, DL-pantolactone, gamma-phenyl-gamma-butyrolactone, gamma-undecalactone, gamma-valerolactone, 2-pentamethylene-1, 3-dioxolan-4-one, gamma-octanedionato-lactone, gamma-caprolactone, gamma-methylumbellate, gamma-methylumbelliferyl-4-one, gamma-valerolactone, gamma-methylumbelliferyl-lactone, gamma-valerolactone, gamma-caprolactone, gamma-valerolactone, and a mixture thereof, α -bromo- γ -butyrolactone, γ -crotonolactone, α -methylene- γ -butyrolactone, α -methacryloyloxy- γ -butyrolactone, β -methacryloyloxy- γ -butyrolactone, and the like.

6-membered ring lactone: for example, delta-valerolactone, delta-caprolactone, delta 0-octalactone, delta 1-nonalactone, delta 2-decalactone, delta-undecalactone, delta-dodecalactone, delta-tridecanolide, delta-tetradecanolide, DL-mevalonolactone, 4-hydroxy-1-cyclohexanecarboxylic acid delta-lactone, monomethyl-delta-valerolactone, monoethyl-delta-valerolactone, monohexyl-delta-valerolactone, 1, 4-bis-valerolactone

Alk-2-ones, 1, 5-dioxepan-2-ones, and the like.

7-membered ring lactone: for example, non-alkyl-epsilon-caprolactone, dialkyl-epsilon-caprolactone, monomethyl-epsilon-caprolactone, monoethyl-epsilon-caprolactone, monohexyl-epsilon-caprolactone, dimethyl-epsilon-caprolactone, di-n-propyl-epsilon-caprolactone, di-n-hexyl-epsilon-caprolactone, trimethyl-epsilon-caprolactone, triethyl-epsilon-caprolactone, tri-n-epsilon-caprolactone, 5-nonyl-oxepan-2-one, 4, 6-trimethyl-oxepan-2-one, 4,6, 6-trimethyl-oxepan-2-one, 5-hydroxymethyl-oxepan-2-one, and the like.

An 8-membered ring lactone: for example, ζ -heptalactone and the like.

Other lactones: for example, lactones, lactides, dilactides, tetramethyl glycosides, 1, 5-dioxepan-2-one, t-butyl caprolactone, and the like.

The cyclic compounds may be used alone or in combination of two or more.

In the present invention, the side chain-introducing compound to be suitably used is a lactone compound, particularly a lactone compound such as e-caprolactone, α -acetyl- γ -butyrolactone, α -methyl- γ -butyrolactone, γ -valerolactone or γ -butyrolactone, and most preferably e-caprolactone.

In addition, when a cyclic compound is reacted by ring-opening polymerization to introduce a side chain, the reactivity of a functional group (for example, a hydroxyl group) bonded to a ring is poor, and it is sometimes difficult to directly react a macromolecule particularly due to steric hindrance or the like. In such a case, for example, the following means can be employed for reacting caprolactone and the like: a functional group (hydroxyl group) having high reactivity is introduced by reacting a low-molecular-weight compound such as propylene oxide with the functional group to thereby hydroxypropylate the compound, and then caprolactone and the hydroxyl group of the hydroxypropyl group are subjected to ring-opening polymerization to introduce a large side chain. In this case, the hydroxypropylated moiety can be considered as a side chain.

In the polyrotaxane (a) used in the present invention, when a side chain having an OH group (hydroxyl group) is introduced into a cyclic molecule, the method of introducing a side chain by the above ring-opening polymerization is preferably employed in consideration of easiness of introduction of a side chain, easiness of adjustment of the size (molecular weight) of a side chain, modification of the OH group, and the like. Therefore, it is preferable to introduce a side chain having an OH group at the terminal.

In addition, a side chain having an active hydrogen group can be introduced by introducing a side chain derived from a cyclic compound such as a cyclic acetal, a cyclic amine, a cyclic carbonate, a cyclic imino ether, or a cyclic thiocarbonate by ring-opening polymerization. Among them, as a specific example of a suitable cyclic compound, a compound described in international publication WO2015/068798 pamphlet can be used.

Further, a method of introducing a side chain into a cyclic molecule by radical polymerization is as follows.

The ring of the cyclic molecule of the polyrotaxane does not have an active site that serves as a radical initiation site. Therefore, before the radical polymerizable compound is reacted, it is necessary to react the compound for forming the radical polymerization initiation point with the functional group (hydroxyl group) of the ring to form an active site serving as the radical initiation point in advance.

Typical examples of the compound for forming such a radical initiation site include organic halogen compounds, such as 2-bromoisobutyl bromide, 2-bromobutyric acid, 2-bromopropionic acid, 2-chloropropionic acid, 2-bromoisobutyric acid, epichlorohydrin, epibromohydrin, and 2-chloroethyl isocyanate. That is, the organohalogen compound is bonded to a ring of a cyclic molecule by a condensation reaction with a functional group of the ring, and a group containing a halogen atom (organohalogen compound residue) is introduced into the ring. In radical polymerization, radicals are generated by movement of halogen atoms on the organic halogen compound residues, and the radicals become radical polymerization initiation points, and radical polymerization proceeds.

In addition, such a group having an active site which becomes a radical polymerization initiation site (organohalogen compound residue) as described above can be introduced as follows: for example, a hydroxyl group of the ring may be reacted with a compound having a functional group such as an amine, a carboxylic acid, an isocyanate, an imidazole, or an acid anhydride to introduce a functional group other than the hydroxyl group, or such a functional group may be reacted with the organic halogen compound.

As the radical polymerizable compound used for introducing a side chain by radical polymerization, a compound having an ethylenically unsaturated bond, for example, a compound having at least 1 kind of functional group such as a (meth) acryloyl group, a vinyl group, a styryl group, or the like (hereinafter referred to as an ethylenically unsaturated monomer) is suitably used. Further, as the ethylenically unsaturated monomer, an oligomer or a polymer having an ethylenically unsaturated bond at the terminal (hereinafter referred to as a macromonomer) may be used. As a specific example of a suitable cyclic compound as such an ethylenically unsaturated monomer, a compound described in International publication WO2015/068798 can be used.

As described above, when a side chain is introduced into a cyclic molecule using a radical polymerizable compound having an active hydrogen group, the side chain becomes a side chain having an active hydrogen-containing group as it is. In addition, when the radical polymerizable compound is not a compound having an active hydrogen-containing group, a part of the side chain may be substituted with an active hydrogen-containing group after the side chain is formed from the radical polymerizable compound.

(constitution of a suitable polyrotaxane (A))

In the present invention, the polyrotaxane (a) to be used most preferably is one obtained by introducing a side chain (terminal is OH group) into a cyclic molecule having an α -cyclodextrin ring, which is a cyclic molecule, by polycaprolactone, using polyethylene glycol having adamantyl groups bonded to both ends thereof as an axial molecule. At this time, OH groups of the α -cyclodextrin ring may be hydroxypropylated and then polycaprolactone may be introduced by ring-opening polymerization.

Next, the polyiso (thio) cyanate compound (B) will be described.

< polyiso (thio) cyanate Compound (B) >

The polyisocyanate (thio) cyanate compound (B) (hereinafter, may be simply referred to as "component (B)") of the present invention is a compound having 2 or more isocyanate groups in 1 molecule, 2 or more isothiocyanate groups in 1 molecule, or 2 or more total groups of isocyanate groups and isothiocyanate groups present in 1 molecule.

The polyiso (thio) cyanate compound (B) may contain a urethane prepolymer (B2) prepared by reacting a polyiso (thio) cyanate compound with a poly (thio) alcohol compound described below. The urethane prepolymer (B2) corresponding to the polyisocyanate (thio) cyanate compound (B) can be used in the present invention without limitation by using a prepolymer containing unreacted isocyanate groups which is generally used.

The polyiso (thio) cyanate compound (B) can be classified into, for example, aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, isothiocyanate compounds and urethane prepolymers (B2). In the present invention, 1 or more of the polyiso (thio) cyanate compound (B) may be used. When a plurality of compounds are used, the reference mass is the total amount of the plurality of compounds. Specifically, the polyiso (thio) cyanate compound (B) includes the following compounds.

Aliphatic isocyanates:

ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2' -dimethylpentane diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1, 3-butadiene-1, 4-diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, 1,6, 11-trimethylundecamethylene diisocyanate, 1,3, 6-trimethylhexamethylene diisocyanate, 1, 8-diisocyanate-4-isocyanatomethyloctane, 2,5, 7-trimethyl-1, 8-diisocyanate-5-isocyanatomethyloctane, 2-functional isocyanate compounds such as bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1, 4-butanediol dipropyl ether-omega, omega' -diisocyanate, lysine diisocyanate methyl ester and 2,4, 4-trimethylhexamethylene diisocyanate (corresponding to the compound containing 2-functional isocyanate (thio) group (B1) constituting the urethane prepolymer (B2) described in detail below)), (meth) acrylic acid esters such as methacrylic acid esters, and the like,

And polyfunctional isocyanate compounds such as lysine triisocyanate, 2-isocyanatoethyl-2, 6-diisocyanatohexanoate, 2-isocyanatopropyl-2, 6-diisocyanatohexanoate and the like.

Alicyclic isocyanate:

isophorone diisocyanate, (bicyclo [2.2.1 ]]Heptane-2, 5-diyl) dimethylene diisocyanate, (bicyclo [2.2.1 ]]Heptane-2, 6-diyl) dimethylene diisocyanate, 2 β,5 α -bis (isocyanate) norbornane, 2 β,5 β -bis (isocyanate) norbornane, 2 β,6 α -bis (isocyanate) norbornane, 2 β,6 β -bis (isocyanate) norbornane, 2, 6-bis (isocyanatomethyl) furan, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane-4, 4 '-diisocyanate, 4-isopropylidenebis (cyclohexylisocyanate), cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2' -dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanate)-n-butylene) pentaerythritol, dimer acid diisocyanate, 2, 5-bis (isocyanatomethyl) -bicyclo [2,2,1]-heptane, 2, 6-bis (isocyanatomethyl) -bicyclo [2,2,1 [ ]]-heptane, 3, 8-bis (isocyanatomethyl) tricyclodecane, 3, 9-bis (isocyanatomethyl) tricyclodecane, 4, 8-bis (isocyanatomethyl) tricyclodecane, 4, 9-bis (isocyanatomethyl) tricyclodecane, 1, 5-diisocyanate decalin, 2, 7-diisocyanate decalin, 1, 4-diisocyanate decalin, 2, 6-diisocyanate decalin, bicyclo [4.3.0]Nonane-3, 7-diisocyanate, bicyclo [4.3.0 ]]Nonane-4, 8-diisocyanate, bicyclo [2.2.1]Heptane-2, 5-diisocyanate and bicyclo [2.2.1]Heptane-2, 6-diisocyanate, bicyclo [2, 2] 2]Octane-2, 5-diisocyanate, bicyclo [2, 2]]Octane-2, 6-diisocyanate, tricyclo [5.2.1.0^2.6]Decane-3, 8-diisocyanate, tricyclo [5.2.1.0^2.6]2-functional isocyanate compounds such as decane-4, 9-diisocyanate (corresponding to the compound containing 2-functional iso (thio) cyanate group (B1) constituting the urethane prepolymer (B2) described in detail below))

2-isocyanatomethyl-3- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) Polyfunctional isocyanate compounds such as bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,1,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6- (2-isocyanatoethyl) -bicyclo [2,2,1] -heptane and 1,3, 5-tris (isocyanatomethyl) cyclohexane.

Aromatic isocyanates:

xylylene diisocyanate (o-, m-, p-), tetrachloro-m-xylylene diisocyanate, methylenediphenyl-4, 4' -diisocyanate, 4-chloro-m-xylylene diisocyanate, 4, 5-dichloro-m-xylylene diisocyanate, 2,3,5, 6-tetrabromo-p-xylylene diisocyanate, 4-methyl-m-xylylene diisocyanate, 4-ethyl-m-xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, 1, 3-bis (α, α -dimethylisocyanatomethyl) benzene, 1, 4-bis (α, α -dimethylisocyanatomethyl) benzene, α, α, α ', α' -tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) butyrate, 2, 6-bis (isocyanatomethyl) furan, phenylene diisocyanates (o-, m-, p-), toluene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, dimethylphenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, 1,3, 5-triisocyanate methylbenzene, 1, 5-naphthalene diisocyanate, methylnaphthalene diisocyanate, biphenyl diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, toluene diisocyanate, 4,4' -diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, 3' -dimethyldiphenylmethane-4, 4' -diisocyanate, dibenzyl-4, 4' -diisocyanate, bis (isocyanatophenyl) ethylene, 3' -dimethoxybiphenyl-4, 4' -diisocyanate, phenylisocyanatomethyl isocyanate, phenylisocyanatoethyl isocyanate, tetrahydronaphthyldiisocyanate, hexahydrophenyldiisocyanate, hexahydrodiphenylmethane-4, 4' -diisocyanate, diphenylether diisocyanate, ethylene glycol diphenylether diisocyanate, 1, 3-propanediol diphenylether diisocyanate, benzophenone diisocyanate, and mixtures thereof, 2-functional isocyanate compounds such as diethylene glycol diphenyl ether diisocyanate, dibenzofuran diisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate, 2, 4-tolylene diisocyanate, and 2, 6-tolylene diisocyanate (corresponding to the compound (B1) containing a 2-functional iso (thio) cyanate group constituting the urethane prepolymer (B2) described in detail below))

Polyfunctional isocyanate compounds such as mesitylene triisocyanate, triphenylmethane triisocyanate, trimellitic acid MDI, naphthalene triisocyanate, diphenylmethane-2, 4,4' -triisocyanate, 3-methyldiphenylmethane-4, 4', 6-triisocyanate, and 4-methyl-diphenylmethane-2, 3, 4', 5, 6-pentaisocyanate.

An isothiocyanate compound:

compounds containing 2-functional isocyanate(s) (corresponding to the compound (B1) containing 2-functional isocyanate (s)) constituting the urethane prepolymer (B2) described in detail below, such as p-phenylenediisothiocyanate, xylylene-1, 4-diisothiocyanate, and ethylenediisothiocyanate.

< suitable polyiso (thio) cyanate Compound (B) >

Among the polyiso (thio) cyanate compounds (B) described above, the following compounds can be suitably used.

Preferred examples of the polyiso (thio) cyanate compound (B) include compounds represented by the following formulae (1) to (7) and 1, 5-naphthalene diisocyanate. In addition to the above, urethane prepolymer (B2) comprising 1, 5-naphthalene diisocyanate, and the isocyanates and polyols shown in the following formulae (1) to (7) is preferably used. Further, preferable examples of the modified iso (thio) cyanate compound sold as a product include carbodiimide-modified MDI (e.g., product name ミリオネート MTL series, manufactured by tokyo co., ltd.), polyol-modified isocyanate (e.g., product names コロネート 1108, コロネート 1120, コロネート 1334, コロネート 1050, コロネート 1057, manufactured by tokyo co., ltd.), and the like. These compounds may be used alone, or 2 or more compounds may be used.

(Compound having alkylene chain)

It is preferable to use a compound represented by the following formula (1):

[ solution 1]

OCN-A-NCO (1)

(wherein A is an alkylene group having 1 to 10 carbon atoms, and may be a group in which a carbon atom in the chain of the alkylene group is replaced by a sulfur atom). The compound represented by the above formula (1) corresponds to the compound (B1) containing a 2-functional isocyanate (thio) cyanate group, which constitutes the urethane prepolymer (B2) described in detail below.

A is an alkylene group having 1 to 10 carbon atoms, and may be a straight-chain or branched-chain group. Among them, preferred is a linear chain of pentamethylene, hexamethylene, heptamethylene, or octamethylene having 5 to 10 carbon atoms, or a branched chain in which a part of hydrogen atoms of pentamethylene, hexamethylene, heptamethylene, or octamethylene is substituted with a methyl group.

Specific examples of the compound represented by the formula (1) include ethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, and 2,4, 4-trimethylhexane methylene diisocyanate. These compounds may be used alone, or 2 or more compounds may be used.

(Compound having 1 phenyl group or cyclohexyl (Ring) group in the molecule)

It is preferable to use a compound represented by the following formula (2) or the following formula (3):

[ solution 2]

[ solution 3]

(wherein, in each of the formulae (2) and (3), 2R's shown¹Each is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and they may be the same or different,

R²is C1-4 alkyl, when there are more than one R²They may be the same or different groups,

a is an integer of 2 or 3, b is an integer of 0 to 4, and c is an integer of 0 to 4. ).

The difference between the compound represented by the above formula (2) and the compound represented by the above formula (3) is the difference between the compound having a phenyl group (the compound represented by the above formula (2)) and the compound having a cyclohexane group (ring) (the compound represented by the above formula (3)). In the compounds represented by the above formula (2) or (3), the case where a is 2 (the case where the isocyanate group is 2 compounds) corresponds to the compound (B1) containing a 2-functional isocyanate (thio) group, which constitutes the urethane prepolymer (B2) described in detail below.

R¹The alkyl group having 1 to 4 carbon atoms in the group (B) may be a straight-chain or branched-chain group. Wherein R is¹Particularly preferred are a hydrogen atom, a methyl group and an ethyl group.

R²In the above formula, the alkyl group having 1 to 4 carbon atoms may be a straight-chain or branched-chain group. Wherein R is²Particularly preferred are a hydrogen atom, a methyl group and an ethyl group.

Specific examples of the compound represented by the formula (2) or the formula (3) include isophorone diisocyanate, xylylene diisocyanate (o-, m-, p-), 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, and phenylene diisocyanate (o-, m-, p-). These compounds may be used alone, or 2 or more of them may be used in combination.

(Compound having 2 phenyl groups or 2 cyclohexyl (ring) groups in the molecule)

It is preferable to use a compound represented by the following formula (4) or the following formula (5):

[ solution 4]

[ solution 5]

(wherein, in each of the formulae (4) and (5), 4 of R are represented³Each is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and they may be the same or different,

d is an integer of 0 to 4. ).

The difference between the compound represented by the above formula (4) and the compound represented by the above formula (5) is the difference between the compound having 2 phenyl groups (the compound represented by the above formula (4)) and the compound having 2 cyclohexane groups (rings) (the compound represented by the above formula (5)). The compound represented by the above formula (4) or (5) corresponds to the compound (B1) containing a 2-functional isocyanate (thio) cyanate group, which constitutes the urethane prepolymer (B2) described in detail below.

R³The alkyl group having 1 to 4 carbon atoms in the group (B) may be a straight-chain or branched-chain group. Wherein R is³Particularly preferred are a hydrogen atom, a methyl group and an ethyl group.

Specific examples of the compound represented by the formula (4) or the formula (5) include 2,2 '-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, 4 '-diphenylmethane diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, and the like. These compounds may be used alone, or 2 or more compounds may be used.

(Compound having a norbornane ring)

A compound represented by the following formula (6):

[ solution 6]

(in the formula, wherein,

R⁴each is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, which may be the same or different, and e is an integer of 0 to 4). The compound represented by the above formula (6) corresponds to the compound (B1) containing a 2-functional isocyanate (thio) cyanate group, which constitutes the urethane prepolymer (B2) described in detail below.

R⁴The alkyl group having 1 to 4 carbon atoms in the group (B) may be a straight-chain or branched-chain group. Wherein R is⁴Particularly preferred are a hydrogen atom, a methyl group and an ethyl group.

Specific examples of the compound represented by the formula (6) include norbornane diisocyanate, 2, 5-bis (isocyanotomethyl) -bicyclo [2,2,1] -heptane, and 2, 6-bis (isocyanotomethyl) -bicyclo [2,2,1] -heptane. These compounds may be used alone, or 2 or more compounds may be used.

(high molecular weight Compound)

A compound represented by the following formula (7):

[ solution 7]

(wherein, 2R are shown⁵Each is an alkyl group having 1 to 4 carbon atoms, which may be the same or different, and f is an integer of 1 to 100).

R⁵The alkyl group having 1 to 4 carbon atoms in the group (B) may be a straight-chain or branched-chain group. Wherein R is⁵Methyl and ethyl are particularly preferred.

Specifically, the compound represented by the above formula (7) is exemplified by polymeric MDI, for example, available under the trade name ミリオネート MR series, available from Tosoh corporation. These compounds may be used alone, or 2 or more compounds may be used.

(particularly suitable polyiso (thio) cyanate compound (B))

Among the preferred iso (thio) cyanates described above, a more suitable iso (thio) cyanate compound includes an aromatic isocyanate and a modified product thereof (urethane prepolymer (B2)). Among these, the urethane prepolymer (B2) is particularly preferably used.

(particularly suitable polyiso (thio) cyanate compound (B): urethane prepolymer (B2))

In the present invention, as the polyisocyanate (B), it is preferable to use a urethane prepolymer (B2) having an isocyanate (thio) group at a molecular end, which is obtained by reacting a 2-functional active hydrogen-containing compound (C1) having 2 active hydrogen-containing groups in the molecule with a 2-functional isocyanate (thio) group-containing compound (B1) having 2 isocyanate (thio) groups in the molecule.

The above-mentioned 2-functional active hydrogen-containing compound (C1) is contained in an active hydrogen-containing compound (C) described in detail below, and corresponds to a compound having 2 active hydrogen-containing groups in the molecule.

Among the compounds described in the polyisocyanate (B), the compound (B1) containing 2-functional isocyanate (thio) cyanate groups corresponds to a compound having 2 isocyanate (thio) cyanate groups in the molecule.

In the present invention, it is preferable to use, as the polyiso (thio) cyanate ester compound (B), a urethane prepolymer (B2) obtained by reacting the 2-functional isocyanate (thio) group-containing compound (B1) with the 2-functional active hydrogen-containing compound (C1). That is, although the following description is made in the context of the polymerization method, it is preferable that the urethane prepolymer (B2) is first prepared, and then the urethane prepolymer (B2) is reacted (polymerized) with the polyrotaxane (a) and, if necessary, an active hydrogen-containing compound (C) described in detail below to produce a urethane resin (hereinafter, this method may be referred to as a "prepolymer method"). When the urethane prepolymer (B2) is reacted (polymerized) with the polyrotaxane (a) and, if necessary, an active hydrogen-containing compound (C) described in detail below, 2 or more kinds of prepolymers having different components and different molecular weights, for example, can be used in combination with the urethane prepolymer (B2). When the prepolymer (B2) is used, another polyiso (thio) cyanate compound (B) may be used together as needed.

When the urethane prepolymer (B2) is prepared, the compound (B1) containing 2-functional isocyanate (thio) groups is not particularly limited, and the compounds exemplified below are particularly preferably used. Specifically, 1, 5-naphthalene diisocyanate, xylylene diisocyanate (o-, m-, p-), 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, phenylene diisocyanate (o-, m-, p-), 2' -diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, 4' -diphenylmethane diisocyanate are preferably used.

On the other hand, the 2-functional active hydrogen-containing compound (C1) is not particularly limited as long as it has 2 active hydrogen-containing groups (-OH, amino group, etc.) in the molecule, among the active hydrogen-containing compounds (C) described in detail below. Among these, as the 2-functional active hydrogen-containing compound constituting the urethane prepolymer (B2), the following compounds are particularly preferably used. Specifically, the following compounds may be mentioned:

a compound having only (2 in the molecule) hydroxyl groups at both ends of the molecule of the polyester polyol, a compound having only (2 in the molecule) hydroxyl groups at both ends of the molecule of the polyether polyol, and a polyester polyol,

A compound having only (2) hydroxyl groups at both ends of the polycaprolactone polyol molecule,

A compound having only (2 in the molecule) hydroxyl groups at both ends of the polycarbonate polyol molecule,

Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, 1, 5-dihydroxypentane, 1, 6-dihydroxyhexane, 1, 7-dihydroxyheptane, 1, 8-dihydroxyoctane, 1, 9-dihydroxynonane, 1, 10-dihydroxydecane, 1, 11-dihydroxyundecane, 1, 12-dihydroxydodecane, neopentyl glycol.

Among them, in order to exhibit particularly excellent characteristics of the finally obtained urethane resin, it is preferable to produce the urethane prepolymer (B2) by using at least 1 2-functional active hydrogen-containing compound (C1) having a molecular weight (number average molecular weight) of 500 to 2000. The 2-functional active hydrogen-containing compound (C1) having a molecular weight of 500 to 2000 may be used in combination with different types of compounds having different molecular weights. In order to adjust the hardness of the finally obtained urethane resin, the 2-functional active hydrogen-containing compound (C1) having a molecular weight (number average molecular weight) of 500 to 2000 and the 2-functional active hydrogen-containing compound (C1) having a molecular weight (number average molecular weight) of 90 to 300 may be used in combination in forming the urethane prepolymer (B2). In this case, although it varies depending on the kind of the 2-functional active hydrogen-containing compound (C1) and the polyiso (thio) cyanate compound (B) used and the amount of the compound used, when the 2-functional active hydrogen-containing compound (C1) having a molecular weight of 500 to 2000 is taken as 100 parts by mass, the 2-functional active hydrogen-containing compound (C1) having a molecular weight of 90 to 300 is preferably 1 to 100 parts by mass.

In addition, both ends of the molecule of the urethane prepolymer (B2) must be isocyanate (thio) groups. Therefore, the urethane prepolymer (B2) is preferably produced by adjusting the number of moles of isocyanate (thio) groups (n1) in the compound (B1) containing 2-functional isocyanate (thio) groups and the number of moles of active hydrogen (n2) in the compound (C1) containing 2-functional active hydrogen to 1< (n1)/(n2) ≦ 2.3. When 2 or more compounds (B1) containing an isocyanate (thio) group at the molecular end are used, the number of moles of the isocyanate (thio) group (n1) is set to the number of moles of the total isocyanate (thio) groups in the isocyanate (thio) group-containing compounds (B1). When 2 or more compounds (C1) containing 2-functional active hydrogen are used, the number of active hydrogen moles (n2) is defined as the number of active hydrogen moles in the total of the compounds containing 2-functional active hydrogen.

As described in detail below, in the case of the compound having an amino group in the compound containing 2-functional active hydrogen (C1), the number of moles of the amino group is equal to the number of moles of the active hydrogen.

The isocyanate equivalent weight (value obtained by dividing the molecular weight of the urethane prepolymer (B2) by the number of isocyanate groups in 1 molecule) of the isocyanate (thio) group of the urethane prepolymer (B2) is preferably 300 to 5000, more preferably 500 to 3000, and particularly preferably 700 to 2000. The urethane prepolymer (B2) in the present invention is preferably a linear prepolymer synthesized from a compound containing 2-functional isocyanate (thio) groups (B1) and a compound containing 2-functional active hydrogen (C1), and therefore the number of isocyanate (thio) groups in 1 molecule is 2 in this case.

When the urethane prepolymer (B2) is used, the urethane prepolymer (B2) and the compound (B1) containing a 2-functional isocyanate (thio) group may be used in combination. In this case, the iso (thio) cyanate equivalent is also preferably 300 to 5000. That is, the polyisocyanate compound (B) comprising the urethane prepolymer (B2) and the compound (B1) containing 2-functional isocyanate (thio) groups preferably has an average isocyanate (thio) cyanate equivalent of 300 to 5000. It is considered that when the average iso (thio) cyanate equivalent is 300 to 5000, the polyiso (thio) cyanate compound (B) having a certain molecular weight is used, and excellent effects are exhibited.

Among them, in the present invention, it is preferable to produce the urethane prepolymer (B2) in the range of 1< (n1)/(n2) ≦ 2 and to produce the urethane prepolymer in a state not including the compound (B1) containing a 2-functional isocyanate (thio) group. That is, the polyiso (thio) cyanate compound (B) composed only of the urethane prepolymer (B2) is used, and the iso (thio) cyanate equivalent of the urethane prepolymer (B2) is preferably 300 to 5000.

The iso (thio) cyanate equivalent of the urethane prepolymer (B2) can be determined by quantifying the iso (thio) cyanate contained in the urethane prepolymer (B2) according to JIS K7301. The amount of the isocyanate group can be determined by the following inverse titration method. First, the obtained urethane prepolymer (B2) was dissolved in a dry solvent. Subsequently, di-n-butylamine having a known concentration which is significantly in excess of the amount of the isocyanate group of the urethane prepolymer (B) is added to the drying solvent, and all the isocyanate groups of the urethane prepolymer (B2) are reacted with di-n-butylamine. Subsequently, the unconsumed (not involved in the reaction) di-n-butylamine was titrated with an acid to determine the amount of consumed di-n-butylamine. Since the consumed di-n-butylamine is equivalent to the isocyanate group of the urethane prepolymer (B2), the isocyanate equivalent weight can be determined. Since the urethane prepolymer (B2) is a linear urethane prepolymer having isocyanate (thio) groups at both ends, the number average molecular weight of the urethane prepolymer (B2) is 2 times the equivalent weight of the isocyanate (thio) ester. The molecular weight of the urethane prepolymer (2) is easily matched with a value measured by Gel Permeation Chromatography (GPC). When the urethane prepolymer (B2) and the compound containing 2-functional isocyanate (thio) group (B1) are used in combination, a mixture of the two may be measured by the above-described method.

The reason why the iso (thio) cyanate equivalent of the urethane prepolymer (B2) is preferably 300 to 5000, more preferably 500 to 3000, and particularly preferably 700 to 2000 is not clear, but it is considered as follows. That is, it is considered that the urethane prepolymer (B2) having a certain molecular weight reacts with the hydroxyl group or the like of the side chain of the polyrotaxane (a) to increase the number of slidable molecules and increase the movement of the molecules themselves, and as a result, the urethane prepolymer is easily restored to deformation (elastic recovery; low hysteresis effect). Further, it is considered that the use of the urethane prepolymer (B2) facilitates the dispersion of the crosslinking points in the urethane resin, and the crosslinking points are randomly and uniformly present, thereby exhibiting stable performance. Accordingly, it is considered that the urethane resin obtained using the urethane prepolymer (B2) can be easily controlled in the production and can be suitably used as a polishing pad. When the urethane prepolymer (B2) and the compound containing a 2-functional isocyanate (thio) group (B1) are used in combination, such an effect can be exhibited even when the polyiso (thio) cyanate compound has an average iso (thio) cyanate equivalent of 300 to 5000. Among these, the above effect is considered to be more remarkable in the case of only the urethane prepolymer (B2).

Further, in the urethane prepolymer (B2), it is preferable that the content ((I); molar mass concentration (mol/kg)) of iso (thio) cyanate present in the urethane prepolymer (B2) determined from the iso (thio) cyanate equivalent of the urethane prepolymer (B2) and the content ((U); molar mass concentration (mol/kg)) of (thio) urethane bonds (containing (thio) urethane bonds) present in the urethane prepolymer (B2) are in the range of 1. ltoreq. (. ltoreq.) (U)/(I). ltoreq.10. This range is the same as the case where the urethane prepolymer (B2) and the compound having 2-functional isocyanate (thio) group (B1) are used in combination. Among them, in the present invention, only the urethane prepolymer (B2) is preferable. The reason is not clear, and the presence of a (thio) urethane bond (containing a (thio) urethane bond) makes it easy for the (thio) urethane bond to interact with other molecules by the action of a hydrogen bond or the like, and improves the properties of the resulting urethane resin. The iso (thio) cyanate content ((I); molar mass concentration (mol/kg)) is the value obtained by multiplying the reciprocal number of the iso (thio) cyanate equivalent by 1000. The content of (thio) urethane bonds (containing (thio) urethane bonds) in the urethane prepolymer ((U) mass molar concentration (mol/kg)) can be determined as follows, for example. That is, when the content of isocyanate (thio) cyanate groups present before the reaction in the compound (C1) containing 2-functional active hydrogen and the compound (B1) containing 2-functional isocyanate (thio) cyanate groups constituting the urethane prepolymer (B2) is defined as the total isocyanate content ((aI); molar mass concentration (mol/kg)), the (thio) urethane bond (containing a (thio) urethane bond) content ((U); molar mass concentration (mol/kg)) is a value ((U) ═ aI) - (I)) obtained by subtracting the isocyanate content ((I); molar mass concentration (mol/kg)) from the total isocyanate (thio) cyanate group content ((aI); molar mass concentration (mol/kg)) of the component (B).

(other Components contained in the polymerizable composition)

The urethane resin for polishing of the present invention is obtained by polymerizing a polymerizable composition containing the polyrotaxane (a) and the polyiso (thio) cyanate compound (B). In the present invention, the polymerizable composition may contain other components in addition to the 2 components described above.

The polymerization-related component may contain an active hydrogen-containing compound (C) having an active hydrogen-containing group other than the polyrotaxane (A). Next, the active hydrogen-containing compound (C) will be described.

< Compound (C) containing active Hydrogen >

The active hydrogen-containing compound (C) (hereinafter, may be simply referred to as "component (C)") used in the present invention is a compound having an active hydrogen-containing group other than the polyrotaxane (a). Examples of the active hydrogen-containing group include the same groups as described in the item (side chain of the cyclic molecule of the polyrotaxane (a)).

The polymerizable composition used in the present invention can adjust the crosslinking density of the obtained urethane resin by containing the component (C). As a result, the obtained urethane resin is considered to exhibit excellent effects.

The active hydrogen-containing compound (C) is not particularly limited as long as it is a compound having 1 or more of the above-mentioned active hydrogen-containing groups. In addition, 1 molecule may have a plurality of active hydrogen-containing groups. Further, various compounds can be used for the active hydrogen-containing compound (C). When a plurality of compounds are used, the reference mass is the total amount of the plurality of compounds. Examples of the active hydrogen-containing compound (C) used in the present invention include the following compounds.

(active hydrogen-containing Compound (C); Compound having OH group)

Examples of the compound having an OH group include a polyol compound. The polyol compound is a compound containing 2 or more OH groups in 1 molecule.

Examples of the compound include compounds having OH groups at both ends of an alkylene group having 2 to 10 carbon atoms, and specific examples thereof include dimethyl-, trimethyl-, tetramethyl-, pentamethyl-, and hexamethyl-dihydroxy compounds. In addition, typical examples thereof include polyesters (polyester polyols) having 2 or more OH groups in 1 molecule, polyethers (hereinafter referred to as polyether polyols) having 2 or more OH groups in 1 molecule, polycarbonates (polycarbonate polyols) having 2 or more OH groups in 1 molecule, polycaprolactones (polycaprolactone polyols) having 2 or more OH groups in 1 molecule, and acrylic polymers (polyacrylic polyols) having 2 or more OH groups in 1 molecule.

In addition, these polyol compounds may also include prepolymers prepared by reacting with the aforementioned polyiso (thio) cyanate compound (B). Among the active hydrogen-containing compounds (C), known compounds having unreacted OH groups at both ends can be used as the prepolymer of the polyol compound.

These compounds are specifically exemplified as follows.

Aliphatic alcohols:

2-functional active hydrogen-containing compounds (corresponding to the 2-functional active hydrogen-containing compound (C1) constituting the urethane prepolymer (B2)), such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1, 5-dihydroxypentane, 1, 6-dihydroxyhexane, 1, 7-dihydroxyheptane, 1, 8-dihydroxyoctane, 1, 9-dihydroxynonane, 1, 10-dihydroxydecane, 1, 11-dihydroxyundecane, 1, 12-dihydroxydodecane, neopentyl glycol, glycerol monooleate, monoceramate, polyethylene glycol, 3-methyl-1, 5-dihydroxypentane, dihydroxyneopentyl, 2-ethyl-1, 2-dihydroxyhexane, and 2-methyl-1, 3-dihydroxypropane,

Examples of the polyfunctional active hydrogen-containing compound include compounds having a polyfunctional active hydrogen such as glycerol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, trimethylolpropane triperoxyethylene ether (for example, TMP-30, TMP-60, TMP-90, etc. from Japanese emulsifier Co., Ltd.), butanetriol, 1, 2-methylglucoside, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabitol, xylitol, adonitol, mannitol, galactitol, iditol, glycol, inositol, hexanetriol, triglycerol, diglycerol, and triethylene glycol.

Alicyclic alcohol:

hydrogenated bisphenol A, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5,2,1,0 ]^2,6]Decane-dimethanol, bicyclo [4,3,0 ]]Nonanediol, bicyclohexanediol, tricyclo [5,3,1^3,9]Dodecanediol, bicyclo [4,3,0 ]]Nonane dimethanol, tricyclo [5,3, 1]^3,9]Dodecane-diethanol, hydroxypropyl tricyclo [5,3,1^3,9]Dodecanol, spiro [3, 4]]2-functional active hydrogen-containing compounds such as octanediol, butylcyclohexanediol, 1' -dicyclohexyldiol, 1, 4-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, and o-dihydroxyxylylene (corresponding to the 2-functional active hydrogen-containing compound (C1) constituting the urethane prepolymer (B2)),

polyfunctional active hydrogen-containing compounds such as tris (2-hydroxyethyl) isocyanurate, cyclohexanetriol, sucrose, maltitol, lactitol and the like.

Aromatic alcohol:

dihydroxynaphthalene, dihydroxybenzene, bisphenol A, bisphenol F, xylylene glycol, tetrabromobisphenol A, bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 1, 2-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, 2-bis (4-hydroxyphenyl) butane, 1-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) -3-methylbutane, tetrabromobisphenol A, bisphenol F, xylylene glycol, tetrabromobisphenol A, and mixtures thereof, 2, 2-bis (4-hydroxyphenyl) pentane, 3-bis (4-hydroxyphenyl) pentane, 2-bis (4-hydroxyphenyl) hexane, 2-bis (4-hydroxyphenyl) octane, 2-bis (4-hydroxyphenyl) -4-methylpentane, 2-bis (4-hydroxyphenyl) heptane, 4-bis (4-hydroxyphenyl) heptane, 2-bis (4-hydroxyphenyl) tridecane, 2-bis (4-hydroxyphenyl) octane, 2-bis (3-methyl-4-hydroxyphenyl) propane, 2-bis (3-ethyl-4-hydroxyphenyl) propane, 2-bis (3-n-propyl-4-hydroxyphenyl) propane, 2, 2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2-bis (3-sec-butyl-4-hydroxyphenyl) propane, 2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2-bis (3-allyl-4' -hydroxyphenyl) propane, 2-bis (3-methoxy-4-hydroxyphenyl) propane, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 2-bis (2,3,5, 6-tetramethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) cyanomethane, methyl ether, ethyl ether, methyl ether, ethyl, 1-cyano-3, 3-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) hexafluoropropane, 1-bis (4-hydroxyphenyl) cyclopentane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) cycloheptane, 1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1-bis (3, 5-dimethyl-4-hydroxyphenyl) cyclohexane, 1-bis (3, 5-dichloro-4-hydroxyphenyl) cyclohexane, 1-bis (3-methyl-4-hydroxyphenyl) -4-methylcyclohexane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 2-bis (4-hydroxyphenyl) norbornane, 2-bis (4-hydroxyphenyl) adamantane, 4' -dihydroxydiphenyl ether, 4' -dihydroxy-3, 3' -dimethyldiphenyl ether, ethylene glycol bis (4-hydroxyphenyl) ether, 4' -dihydroxydiphenyl sulfide, 3' -dimethyl-4, 4' -dihydroxydiphenyl sulfide, 3' -dicyclohexyl-4, 4' -dihydroxydiphenyl sulfide, 3' -diphenyl-4, 4' -dihydroxydiphenyl sulfide, 4' -dihydroxydiphenyl sulfoxide, 3' -dimethyl-4, 4' -dihydroxydiphenyl sulfoxide, 2-bis (4-hydroxyphenyl) norbornane, 2-bis (4-hydroxyphenyl) adamantane, 4' -dihydroxydiphenyl ether, 4, 3' -dihydroxydiphenyl sulfide, 3' -dicyclohexyl-4, 4' -dihydroxydiphenyl sulfide, 3' -dihydroxydiphenyl sulfoxide, 4' -dihydroxydiphenyl sulfoxide, 2,4' -dihydroxydiphenyl-dimethyldiphenyl sulfide, 4' -dihydroxydiphenyl sulfide, ethylene glycol bis (4-hydroxyphenyl) adamantane, 4-hydroxyphenyl) ether, 4-bis (4-hydroxyphenyl) adamantane, 4-dihydroxydiphenyl sulfide, ethylene glycol, 2, 4-dihydroxydiphenyl sulfide, 4-bis (2, 4-dihydroxydiphenyl sulfide), 2, 4-dihydroxydiphenyl sulfide, 3, 4-dihydroxydiphenyl sulfide, 4-dihydroxy-diphenyl sulfide, 4-dihydroxy diphenyl sulfide, 3, or a, 4,4' -dihydroxydiphenylsulfone, 4,4' -dihydroxy-3, 3' -dimethyldiphenylsulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3-methylphenyl) ketone, 7' -dihydroxy-3, 3',4,4' -tetrahydro-4, 4,4',4' -tetramethyl-2, 2' -spirobis (2H-1-benzopyran), trans-2, 3-bis (4-hydroxyphenyl) -2-butene, 9-bis (4-hydroxyphenyl) fluorene, 3-bis (4-hydroxyphenyl) -2-butanone, 1, 6-bis (4-hydroxyphenyl) -1, 6-hexanediol, hexane diol, and hexane diol, 4,4' -dihydroxybiphenyl, m-dihydroxyxylylene, p-dihydroxyxylylene, 1, 4-bis (2-hydroxyethyl) benzene, 1, 4-bis (3-hydroxypropyl) benzene, 1, 4-bis (4-hydroxybutyl) benzene, 1, 4-bis (5-hydroxypentyl) benzene, 1, 4-bis (6-hydroxyhexyl) benzene, 2-bis [4- (2 "-hydroxyethoxy) phenyl ] propane, and 2-functional active hydrogen-containing compounds such as hydroquinone and resorcinol (corresponding to the 2-functional active hydrogen-containing compound (C1) constituting the urethane prepolymer (B2)), a salt thereof, a water-soluble organic solvent, and a water-soluble organic solvent,

And compounds containing multifunctional active hydrogen such as trihydroxy naphthalene, tetrahydroxy naphthalene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxy phenanthrene, and the like.

Polyester polyol: examples thereof include compounds obtained by condensation reaction of polyhydric alcohols and polybasic acids. Among them, the number average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 1200. The compound having only (2 in the molecule) hydroxyl groups at both ends of the molecule corresponds to the 2-functional active hydrogen-containing compound (C1) constituting the urethane prepolymer (B2).

Polyether polyol: examples thereof include compounds obtained by ring-opening polymerization of alkylene oxides, or by reaction of a compound having 2 or more active hydrogen-containing groups in the molecule and alkylene oxides, and modifications thereof. Among them, the number average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 1200. The compound having only (2 in the molecule) hydroxyl groups at both ends of the molecule corresponds to the 2-functional active hydrogen-containing compound (C1) constituting the urethane prepolymer (B2).

Polycaprolactone polyol: examples thereof include compounds obtained by ring-opening polymerization of epsilon-caprolactone. Among them, the number average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 1200. The compound having only (2 in the molecule) hydroxyl groups at both ends of the molecule corresponds to the 2-functional active hydrogen-containing compound (C1) constituting the urethane prepolymer (B2).

Polycarbonate polyol: examples thereof include a compound obtained by phosgenating 1 or more kinds of low-molecular-weight polyhydric alcohols, and a compound obtained by transesterification using ethylene carbonate, diethyl carbonate, diphenyl carbonate, or the like. Among them, the number average molecular weight is preferably 400 to 2000, more preferably 500 to 1500, and most preferably 600 to 1200. The compound having only (2 in the molecule) hydroxyl groups at both ends of the molecule corresponds to the 2-functional active hydrogen-containing compound (C1) constituting the urethane prepolymer (B2).

Polyacrylic acid polyol: examples thereof include compounds obtained by copolymerizing hydroxyl group-containing acrylic acid esters or methacrylic acid esters with monomers copolymerizable with these esters. The compound having only (2 in the molecule) hydroxyl groups at both ends of the molecule corresponds to the 2-functional active hydrogen-containing compound (C1) constituting the urethane prepolymer (B2).

Acrylic polyol: examples of the polyol compound include polyol compounds obtained by polymerizing a (meth) acrylate or a vinyl monomer. The compound having only (2 in the molecule) hydroxyl groups at both ends of the molecule corresponds to the 2-functional active hydrogen-containing compound (C1) constituting the urethane prepolymer (B2).

In addition, in the active hydrogen-containing compound (C), examples of the compound having an OH group include a monool compound in addition to a polyol compound. The monoalcohol compound has 1 OH group in 1 molecule. These compounds are specifically exemplified as follows.

A mono-alcohol compound: examples thereof include polyethylene glycol monooleate, polyoxyethylene monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol mono-4-octylphenyl ether, linear polyoxyethylene alkyl ethers (polyethylene glycol monomethyl ether, polyoxyethylene lauryl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether), polypropylene glycol monomethyl ether, glycerol dioleate, and linear or branched saturated alkyl alcohols having 5 to 30 carbon atoms.

The above-exemplified compounds may be those having an OH group during the reaction. That is, in the reaction field, a compound having a group which can form an OH group, specifically, a compound having an ethoxy group may be mentioned.

In the present invention, among the above compounds, a polyol compound having 2 or 3 OH groups in the molecule is preferably used. As the compound other than the diol compound, a monoalcohol compound having 1 OH group in the molecule is preferably used.

(active hydrogen-containing Compound (C): SH group-containing Compound)

Next, an active hydrogen-containing compound (C) having an SH group (thiol group) is exemplified. Examples of the compound having an SH group include polythiol compounds. The polythiol compound is a compound containing 2 or more SH groups in 1 molecule. These polythiol compounds may contain a prepolymer prepared by reacting with the polyiso (thio) cyanate compound (B) as described above, in the same manner as the polyol compound described above. (As the prepolymer of the polythiol compound containing the active hydrogen compound (C), a prepolymer containing unreacted SH groups which is generally used in the present invention may be used).

These compounds are specifically exemplified as follows.

Aliphatic thiol compounds:

2-functional active hydrogen-containing compounds (corresponding to the 2-functional active hydrogen-containing compound (C1) constituting the urethane prepolymer (B2)) such as 1, 3-propanedithiol, 1, 6-hexanedithiol, 1, 10-decanedithiol, 1, 8-octanedithiol, 1, 4-butanediol bis (3-mercaptopropionate), 1, 4-butanediol bis (thioglycol), 1, 6-hexanediol bis (thioglycol), tetraethylene glycol bis (3-mercaptopropionate), and 1, 6-hexanediol bis (3-mercaptopropionate), and the like, and also includes,

Polyfunctional active hydrogen-containing compounds such as tetrakis (mercaptomethyl) methane, trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), and pentaerythritol tetrakis (3-mercaptobutyrate).

Alicyclic thiol compounds: 1, 4-bis (mercaptopropylthiomethyl) benzene, and 2, 5-bis (mercaptomethyl) -1, 4-dithiane, and the like. They correspond to compounds containing 2-functional active hydrogens (C1).

Aromatic thiol compounds: 4, 6-bis (mercaptomethylthio) -1, 3-dithiane.

Examples of the other SH group-containing compound include monothiol compounds. The monothiol compound may have 1 thiol group in 1 molecule, and these compounds are exemplified specifically as follows.

Monothiol compound: 3-methoxybutyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, and saturated alkyl mercaptans having a linear or branched structure with 5 to 30 carbon atoms.

Hereinafter, compounds having an amino group are exemplified.

(active hydrogen-containing Compound (C): amino-containing Compound (CA))

The compound having a primary or secondary amino group of the present invention can be used without any limitation. Among them, they are roughly classified into aliphatic amines, alicyclic amines, aromatic amines, and polyamine compounds, and specific examples thereof include the following compounds.

Aliphatic amine:

2-functional active hydrogen-containing compounds such as ethylenediamine, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, m-xylylenediamine, 1, 3-propanediamine, and putrescine (corresponding to the 2-functional active hydrogen-containing compound (C1) constituting the urethane prepolymer (B2)),

polyfunctional active hydrogen-containing compounds such as diethylenetriamine,

Monofunctional active hydrogen-containing compounds such as butylamine, hexylamine, dodecylamine, octylamine, diethylamine, di-N-propylamine, diisopropylamine, di-N-butylamine, diisobutylamine, di-t-butylamine, dihexylamine, di (2-ethylhexyl) amine, N-isopropyl-N-isobutylamine, di-sec-butylamine, and N-methylhexylamine.

Alicyclic amine: 2-functional active hydrogen-containing compounds such as isophoronediamine and cyclohexyldiamine (corresponding to the 2-functional active hydrogen-containing compound (C1) constituting the urethane prepolymer (B2))

And monofunctional active hydrogen-containing compounds such as cyclohexylamine.

Aromatic amine:

4,4 '-methylenebis (o-chloroaniline) (MOCA), 2, 6-dichloro-p-phenylenediamine, 4' -methylenebis (2, 3-dichloroaniline), 4 '-methylenebis (2-ethyl-6-methylaniline), 3, 5-bis (methylthio) -2, 4-toluenediamine, 3, 5-bis (methylthio) -2, 6-toluenediamine, 3, 5-diethyltoluene-2, 4-diamine, 3, 5-diethyltoluene-2, 6-diamine, trimethylene glycol-di-p-aminobenzoate, polytetramethylene glycol-di-p-aminobenzoate, 4' -diamino-3, 3', 5,5 ' -tetraethyldiphenylmethane, 4' -diamino-3, 3' -diisopropyl-5, 5 ' -dimethyldiphenylmethane, 4' -diamino-3, 3', 5,5 ' -tetraisopropyldiphenylmethane, 1, 2-bis (2-aminophenylthio) ethane, 4' -diamino-3, 3' -diethyl-5, 5 ' -dimethyldiphenylmethane, N ' -di-sec-butyl-4, 4' -diaminodiphenylmethane, 3' -diethyl-4, 4' -diaminodiphenylmethane, m-xylylenediamine, N ' -di-sec-butyl-p-phenylenediamine, m-xylylenediamine, N ' -di-sec-butyl-p-phenylenediamine, N-xylylenediamine, and mixtures thereof, Compounds having 2-functional active hydrogen such as p-xylylenediamine, p-phenylenediamine, 3' -methylenebis (methyl-6-aminobenzoate), 2-methylpropyl 2, 4-diamino-4-chlorobenzoic acid, isopropyl 2, 4-diamino-4-chlorophenylacetic acid, bis- (2-aminophenyl) thioethyl terephthalate, diphenylmethanediamine, tolylenediamine, and piperazine (corresponding to the compound (C1) having 2-functional active hydrogen constituting the urethane prepolymer (B2)), a salt thereof, a hydrate thereof, a solid thereof, and a solid,

Polyfunctional active hydrogen-containing compounds such as 1,3, 5-benzenetriamine and melamine,

Monofunctional active hydrogen-containing compounds such as 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, piperidine, 2, 4-dimethylpiperidine, 2, 6-dimethylpiperidine, 3, 5-dimethylpiperidine, morpholine, pyrrole, and N-methylbenzylamine.

These can be used alone, also can be used in combination of more than 2.

Incidentally, in the above-mentioned amino group-containing Compound (CA), strictly speaking, an amino group (-NH-) -₂) Has 2 active hydrogens. In the present invention, the number of moles of active hydrogen in the compound having an amino group is equal to the number of moles of amino groups, taking into consideration the reactivity of active hydrogen in the amino group. The reaction of an amino group with an isocyanate group is shown below: 1 active hydrogen in the amino group reacts with 1 isocyanate (thio) group to form a urethane bond/thiourethane bond first. Next, if the active hydrogen in the bond (-NHCONH-, -NHCSNH-) is not at a high temperature, for example, if it is not at a temperature of 150 ℃ or higher, it is not involved in the subsequent reaction. Thus, in the present invention, substantially 1 mole of an isocyanate (thio) group is reacted with 1 mole of an amino group (1 mole of active hydrogen in the amino group). Therefore, in the present invention, when the compound having an amino group such as the amino group-containing Compound (CA) is used, the number of moles of active hydrogen in the compound having an amino group is equal to the number of moles of the amino group. In addition, it is a matter of course that, in the case of an amino group-containing Compound (CA) having a secondary amino group (e.g., -NHR) that reacts with an isocyanate group, the number of moles of active hydrogen in the amino group-containing compound is also equal to the number of moles of amino groups.

(active hydrogen-containing Compound (C) Compound active Hydrogen-containing Compound)

The complex active hydrogen-containing compound is a compound having a plurality of active hydrogen-containing groups of different kinds in the molecule, and various physical properties can be adjusted by using such an active hydrogen-containing compound.

Examples of such a complex active hydrogen-containing compound include an OH/SH type compound containing an OH group and an SH group, an OH/amino type compound containing an OH group and an amino group, and the like, and specific examples thereof include the following compounds.

OH/SH type compounds:

examples thereof include a 2-functional active hydrogen-containing compound of 1-hydroxy-4-mercaptocyclohexane (corresponding to the 2-functional active hydrogen-containing compound (C1) constituting the urethane prepolymer (B2))

Polyfunctional active hydrogen-containing compounds such as 3-mercapto-1, 2-propanediol, 1, 3-dimercapto-2-propanol, 2, 3-dimercapto-1-propanol, pentaerythritol tris (3-mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), and pentaerythritol bis (3-mercaptopropionate),

Examples of the monofunctional active hydrogen-containing compound include 4-mercaptophenol.

OH/amino type compounds: 2-functional active hydrogen-containing compounds such as monoethanolamine and monopropanolamine (corresponding to the 2-functional active hydrogen-containing compound (C1) constituting the urethane prepolymer (B2)),

multifunctional active hydrogen-containing compounds such as diethanolamine and 2- (2-aminoethylamino) ethanol. They are included in amino group-containing Compounds (CA). It is needless to say that, in these compounds, the number of moles of active hydrogen in the amino group is considered to be equal to that of the amino group, and the number of moles of active hydrogen is considered to be the total number of moles of the amino group and the number of moles of the hydroxyl group.

These can be used alone, also can be used in combination of more than 2.

(suitable active hydrogen-containing Compound (C))

Among the above-mentioned components (C), active hydrogen-containing compounds having OH groups and amino groups are particularly preferable from the viewpoints of reactivity and odor generated when the resulting polyurethane resin is abraded. Among them, differences in the production method of the urethane resin, the optimum component (C), the blending amount thereof, and the like are different. That is, a method for producing a polyurethane resin by simultaneously reacting a polyrotaxane (a), a polyiso (thio) cyanate compound (B) (except for the urethane prepolymer (B2), and an active hydrogen-containing compound (C) (hereinafter, this method may be abbreviated as "one-pot method") is different from the case of producing a urethane resin using the urethane prepolymer (B2). This will be explained next.

(suitable active hydrogen-containing Compound (C) in one-pot method)

In the production of a urethane resin by the one-pot method, an aliphatic polyol (preferably a "polyol" having 3 or more hydroxyl groups in the molecule), or a combination of a polyol having 3 or more hydroxyl groups in the molecule and a diol (a compound having 2 hydroxyl groups in the molecule) is preferable in view of physical properties, ease of handling, and productivity of the urethane resin.

(suitable active hydrogen-containing Compound (C) in the prepolymer method)

On the other hand, in the prepolymer method using the urethane prepolymer (B2), the isocyanate group(s) of the urethane prepolymer (B2) is reacted (polymerized) with the active hydrogen-containing group(s) in the polyrotaxane (a) and the active hydrogen-containing compound (C) to produce a urethane resin having a high molecular weight, and the following active hydrogen-containing compound (C) is preferably used. That is, when the urethane prepolymer (B2) is used, it is preferable to use an amino group-containing Compound (CA) having an amino group. Among the amino group-containing Compounds (CA), 4' -methylenebis (o-chloroaniline) (hereinafter, sometimes simply referred to as "MOCA"), trimethylene glycol-di-p-aminobenzoate, polytetramethylene glycol-di-p-aminobenzoate, and the like are preferably used.

The reason is not clear, but is considered as follows. That is, a urethane resin obtained by a prepolymer method is easy to control the molecular structure, but is difficult to be a resin having a high degree of crosslinking as compared with a one-pot method. In the prepolymer method, the urethane resin obtained by using the above-mentioned amino group-containing Compound (CA) is a urethane urea resin having a urethane bond. It is considered that the urethane bond portions can form a pseudo crosslinked structure by hydrogen bonding between the bonds of the urethane bond, or the urethane bond portions can react with (polymerize) the isocyanate (thio) groups of the urethane prepolymer (B2) to form a crosslinked structure, and therefore the mechanical strength of the obtained urethane resin can be improved.

(compounding ratio of polymerizable composition)

The polymerizable composition used in the present invention is not particularly limited, and preferably contains 3 to 2000 parts by mass of the polyiso (thio) cyanate compound (B) per 100 parts by mass of the polyrotaxane (a) in order to exhibit excellent effects. In the obtained urethane resin, when the proportion of the polyrotaxane (a) is too small, the wear resistance-improving effect by the high mobility which the polyrotaxane (a) originally has tends to be reduced. When the amount of the polyrotaxane (a) is too large, the effect of improving the abrasion resistance by crosslinking tends to be reduced in the same manner. It is also considered that the dispersibility of the polyiso (thio) cyanate compound (B) in the polymerizable composition is lowered, and it tends to be difficult to produce a urethane resin in which crosslinking points are uniformly dispersed. Therefore, the polymerizable composition preferably contains the polyiso (thio) cyanate compound (B) in an amount of 4 to 1500 parts by mass, and more preferably contains the polyiso (thio) cyanate compound (B) in an amount of 5 to 1000 parts by mass, based on 100 parts by mass of the polyrotaxane (a).

(suitable formulation ratio in one-pot method (when active hydrogen-containing compound (C) is not used))

When the polyrotaxane (a) and the polyiso (thio) cyanate compound (B) are reacted by the one-pot method, the amount of the polyiso (thio) cyanate compound (B) is preferably 5 to 50 parts by mass per 100 parts by mass of the polyrotaxane (a) because the polyrotaxane (a) has excellent mechanical properties.

(suitable compounding ratio in the prepolymer method (when the active hydrogen-containing compound (C) is not used))

When the polyrotaxane (a) and the urethane prepolymer (B2) are reacted, the amount of the urethane prepolymer (B2) is preferably 20 to 1000 parts by mass based on 100 parts by mass of the polyrotaxane (a) because the composition is excellent in mechanical properties.

(ratio: when the active hydrogen-containing compound (C) is used)

When the polymerizable composition contains the active hydrogen-containing compound (C), it is preferable that the polyiso (thio) cyanate compound (B) is contained in an amount of 10 to 3000 parts by mass and the active hydrogen-containing compound (C) is contained in an amount of 3 to 2000 parts by mass, based on 100 parts by mass of the polyrotaxane (a). The presence of the polyrotaxane (a) in the urethane resin obtained from the polymerizable composition to some extent exerts an excellent effect. Therefore, the polyiso (thio) cyanate compound (B) is preferably contained in an amount of 15 to 2500 parts by mass and the active hydrogen-containing compound (C) is preferably contained in an amount of 4 to 1000 parts by mass, and the polyiso (thio) cyanate compound (B) is preferably contained in an amount of 20 to 1500 parts by mass and the active hydrogen-containing compound (C) is preferably contained in an amount of 5 to 500 parts by mass, based on 100 parts by mass of the polyrotaxane (A).

(suitable formulation ratio in the one-pot method (when the active hydrogen-containing compound (C) is used))

When the polyrotaxane (a), the polyiso (thio) cyanate compound (B) and the active hydrogen-containing compound (C) are reacted by the one-pot method, the mixing ratio of each is preferably 20 to 500 parts by mass of the polyiso (thio) cyanate compound (B) and 50 to 500 parts by mass of the active hydrogen-containing compound (C) per 100 parts by mass of the polyrotaxane (a), because the mechanical properties are excellent.

(suitable compounding ratio in the prepolymer method (when active hydrogen-containing compound (C) is used))

When the polyrotaxane (a), the urethane prepolymer (B2) and the active hydrogen-containing compound (C) are reacted, the mixing ratio of each is preferably 50 to 1500 parts by mass of the urethane prepolymer (B2) and 5 to 200 parts by mass of the active hydrogen-containing compound (C) per 100 parts by mass of the polyrotaxane (a), because the mechanical properties are excellent.

(particularly preferred blending ratio when the active hydrogen-containing compound (C) is used)

In the polymerizable composition used in the present invention, the appropriate amounts of the respective components are as described above, but in the present invention, it is preferable to adjust the respective components of the polymerizable composition so as to satisfy not only the above-described compounding ratios but also the following conditions. That is, the ratio of the total molar number of the active hydrogen group-containing moles of the polyrotaxane (a) and the active hydrogen group-containing moles of the active hydrogen-containing compound (C) added as necessary (hereinafter, sometimes referred to as "the total active hydrogen group-containing molar number") to the molar number of the isocyanate groups of the polyisocyanate (thio) cyanate compound (B) (in the case of the prepolymer method), is preferably in the following range.

Specifically, the number of moles of all active hydrogen-containing groups is preferably 0.8 to 1.2 moles based on 1 mole of the isocyanate (thio) group. When the amount of the isocyanate group is too large or too small, poor curing or deterioration in abrasion resistance tends to occur in the obtained urethane resin. In order to obtain a urethane resin having a good cured state, a uniform state, and excellent abrasion resistance, the number of moles of all active hydrogen-containing groups is more preferably 0.85 to 1.15 moles, and still more preferably 0.9 to 1.1 moles, based on 1 mole of the isocyanate (thio) group.

When the polymerizable composition does not contain the active hydrogen-containing compound (C), the number of moles of all the active hydrogen-containing groups is equal to the number of moles of the active hydrogen-containing groups of the polyrotaxane (a).

In the case where the active hydrogen-containing compound (C) is contained in the polymerizable composition in the number of moles of all the active hydrogen-containing groups, when the number of moles of the active hydrogen-containing groups of the polyrotaxane (a) is 1, the number of moles of the active hydrogen-containing compound (C) is preferably 0.1 to 20 moles, more preferably 0.2 to 10 moles.

In addition, the "number of moles of all active hydrogen-containing groups" includes all active hydrogen-containing groups of the polyrotaxane (a), that is, active hydrogen-containing groups of the side chain and active hydrogen-containing groups of other sites (for example, active hydrogen-containing groups directly of the cyclic molecule (in the case where the cyclic molecule is an α -cyclodextrin ring, hydroxyl groups of the α -cyclodextrin ring to which the side chain is not introduced)).

However, for example, since the reactivity of a hydroxyl group or the like of an α -cyclodextrin ring to which a side chain is not introduced is low, it is considered that the hydroxyl group is not included. Therefore, the total molar number of active hydrogen-containing groups of the side chain of the polyrotaxane (a) (hereinafter, sometimes referred to as "total molar number of active hydrogen-containing groups") and the total molar number of active hydrogen-containing groups of the active hydrogen-containing compound (C) to be added as needed is preferably 1.2 to 0.4 mol, more preferably 1.2 to 0.6 mol, based on 1mol of the isocyanate (thio) group. By satisfying this range, a urethane resin having a good cured state, a uniform state, and excellent abrasion resistance can be obtained.

As described above, the preferable ratio of the "total number of moles of active hydrogen-containing groups" or the "total number of moles of active hydrogen-containing groups" to the number of moles of the isocyanate group(s) of the polyisocyanate(s) compound (B) is in the same range regardless of whether the one-pot method or the prepolymer method is employed.

It is to be noted that, needless to say, when the "total number of moles of active hydrogen-containing groups" and the "total number of moles of active hydrogen-containing groups" are calculated, when a compound having an amino group such as the amino group-containing Compound (CA) is used as the active hydrogen-containing compound (C), the number of moles of active hydrogen in the compound having an amino group is equal to the number of moles of amino groups.

(method of polymerizing polymerizable composition)

In the present invention, the polymerizable composition may be polymerized to obtain the urethane resin for polishing. The method of polymerization is not particularly limited, and a general method of polymerizing a compound having an active hydrogen-containing group and a compound having an isocyanate (thio) group to obtain a polyurethane resin can be employed. Specifically, a dry method such as a one-pot method or a prepolymer method, a wet method using a solvent, or the like can be used. In the present invention, a dry method is particularly preferably used.

For example, if the polyrotaxane (a) ((a) component) and the polyiso (thio) cyanate compound (B) ((B) component) are simultaneously polymerized in the polymerizable composition by a one-pot method, a urethane resin can be obtained by simultaneously polymerizing the (C) component in the presence of the active hydrogen-containing compound (C) ((C) component). The component (A) may be mixed with the component (C) in advance and then reacted with the component (B) as long as the component (A) is a solid and non-molten component.

In the prepolymer method, for example, the component (B) and the component (C) may be reacted in advance to prepare a urethane prepolymer (B2) having an isocyanate (thio) group at the molecular end, and then the urethane prepolymer and the component (a) may be mixed and reacted with each other. In this case, the urethane prepolymer (B2) may be reacted not only with the component (A) but also with a composition containing the components (B) and (C). When the prepolymer has no isocyanate group and has an active hydrogen-containing group, the active hydrogen-containing prepolymer may be reacted with the components (a) and (B). In this case, in addition to the components (a) and (B), a polymerizable composition may be obtained by reacting a composition containing the component (C) other than the active hydrogen-containing prepolymer with the active hydrogen-containing prepolymer. However, from the viewpoint of controlling the reaction (polymerization), it is preferable to use a urethane prepolymer (B2) having an isocyanate (thio) group at the molecular end. In particular, when the component (C) to be reacted with the urethane prepolymer (B2) is used, the component (C) is preferably an amino group-containing Compound (CA).

(other Properties and additives of the obtained urethane resin)

The urethane resin of the present invention may have fine pores in the resin. In this case, a known foaming method or the like can be used without any limitation. If these methods are exemplifiedThe following methods can be mentioned: a foaming method in which a volatile foaming agent such as a low-boiling hydrocarbon or water is added, a method in which hollow microspheres (microspheres) are dispersed and solidified, a method in which thermally swellable fine particles are mixed and heated to foam the fine particles, or a Mechanical flow foaming method in which an inert gas such as air or nitrogen is blown into the mixture. The density of the urethane resin is preferably 0.4 to 0.9g/cm at the time of foaming³. Further, when foaming with water, the reaction with an isocyanate group results in carbon dioxide and an amino group, and the amino group further reacts with the isocyanate group to form a urethane bond/thiourethane bond. Thus, in the present invention, water is considered to have 2 active hydrogens when used as an additive.

The urethane resin of the present invention can be used for a polishing pad because of its excellent mechanical properties. The urethane resin of the present invention may have any suitable hardness. The hardness can be measured by the Shore (Shore) method, and can be measured, for example, by JIS standard (hardness test) K6253. The urethane resin of the present invention preferably has a shore hardness of 40A to 90D. The shore hardness of a general urethane resin for polishing materials used in the present invention is preferably 20D to 90D, and more preferably 20D to 80D ("D" represents hardness on the scale of shore "D"). When used in applications requiring a relatively soft polishing pad, the urethane resin of the present invention preferably has a shore hardness of 40A to 90A, more preferably 50A to 90A ("a" indicates hardness on the scale of shore "a"). Thus, the hardness can be arbitrarily changed by changing the blending composition and blending amount as necessary.

The polyurethane resin of the present invention is preferable in that it has a compressibility in a certain range and can exhibit flatness of an object to be polished. The compressibility can be measured by a method based on JIS L1096, for example. The compressibility of the urethane resin of the present invention is preferably 0.5% to 50%. Within the above range, excellent flatness of the polished object can be exhibited.

In addition, the polyurethane resin of the present invention can exhibit flatness of an object to be polished and a high polishing rate when used as a polishing pad by having low hysteresis loss property or excellent elastic recovery property. The hysteresis loss can be measured, for example, by a method according to JIS K6251. Specifically, the test piece prepared in a dumbbell shape was recovered after being stretched by 100%, and the hysteresis loss (area of elongation and stress at the time of recovery after stretching/area of elongation and stress at the time of stretching × 100) was measured.

The urethane resin of the present invention is not particularly limited, and the hysteresis loss is preferably 60% or less, more preferably 50% or less, and still more preferably 40% or less. It is presumed that by reducing the hysteresis loss, the kinetic energy of the abrasive grains can be uniformly used for polishing the object to be polished when used as a polishing pad, and thus excellent flatness and a high polishing rate can be exhibited. Further, it is considered that a soft polishing pad can exhibit an excellent polishing rate by reducing hysteresis loss.

In addition, the urethane resin of the present invention may have a polishing layer formed of a plurality of layers. For example, when the urethane resin of the present invention includes 2 layers, the polishing layer may include a 1 st layer having a polishing surface in contact with an object to be polished at the time of polishing, and a 2 nd layer in contact with the 1 st layer on a surface opposite to the polishing surface of the 1 st layer. In this case, the physical properties of the 1 st layer can be adjusted by providing the 2 nd layer with a hardness and an elastic modulus different from those of the 1 st layer. For example, the polishability of the object to be polished can be adjusted by changing the hardness of the 1 st layer and the hardness of the 2 nd layer.

The urethane resin of the present invention may contain abrasive grains as a constituent element, and may be a so-called fixed-abrasive-grain urethane resin. Examples of the abrasive grains include particles made of a material selected from the group consisting of cerium oxide, silicon oxide, aluminum oxide, silicon carbide, zirconium oxide, iron oxide, manganese dioxide, titanium oxide, and diamond, and particles containing 2 or more kinds of these materials. The method for storing these abrasive grains is not particularly limited, and for example, the abrasive grains can be stored in the urethane resin by dispersing the abrasive grains in the polymerizable composition and then curing the polymerizable composition.

In addition, a polymerization catalyst, a stabilizer such as an antioxidant, an ultraviolet absorber, a surfactant, a flame retardant, a plasticizer, a pigment, a filler, an antistatic agent, a foam stabilizer, and other additives may be added to the urethane resin of the present invention. These additives may be used alone, or 2 or more of them may be used in combination. These additives are contained in the polymerizable composition, and the polymerizable composition is polymerized to be contained in the urethane resin for polishing.

The urethane resin of the present invention is not particularly limited, and a groove structure may be formed on the surface thereof. The groove structure is not particularly limited as long as it is a shape capable of holding and renewing the slurry when polishing a member to be polished, and examples thereof include X (stripe) grooves, XY lattice grooves, concentric circular grooves, through holes, non-penetrating holes, polygonal prisms, circular columns, spiral grooves, eccentric circular grooves, radial grooves, and a structure in which these grooves are combined.

The method for forming the trench structure is not particularly limited, and examples thereof include the following: a method of machining using a jig having a pitch of a predetermined size, a method of molding by pouring a resin into a mold having a predetermined surface shape and curing the resin, a method of molding by pressing a resin with a platen having a predetermined surface shape, a method of molding by photolithography, a method of molding by a printing method, a method of molding by a laser such as a carbon dioxide laser, and the like.

The urethane resin of the present invention may be used, for example, as a nonwoven fabric urethane resin polishing pad obtained by impregnating a nonwoven fabric with the urethane resin of the present invention and then curing the impregnated nonwoven fabric.

Examples

The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples and comparative examples, evaluation methods and the like are as follows.

(polyrotaxane (A) to be used)

RX-1: the side chain having a hydroxyl group in the side chain has a weight average molecular weight of about 350 and a weight average molecular weight of 200000.

RX-2: the side chain having a hydroxyl group in the side chain had a polyrotaxane having an average molecular weight of about 650 and a weight average molecular weight of 350000.

RX-3: the side chain having a hydroxyl group in the side chain had an average molecular weight of about 450 and a weight average molecular weight of 300000.

(molecular weight measurement: gel permeation chromatography (GPC measurement))

GPC measurement was carried out using a liquid chromatography apparatus (manufactured by Japan ウォーターズ). The column used is preferably Shodex GPC KF-802 (exclusion limit molecular weight: 5,000), KF802.5 (exclusion limit molecular weight: 20,000), KF-803 (exclusion limit molecular weight: 70,000), KF-804 (exclusion limit molecular weight: 400,000), KF-805 (exclusion limit molecular weight: 2,000,000) manufactured by Shorey and electrician, depending on the molecular weight of the sample analyzed. Further, Dimethylformamide (DMF) was used as a developing solution, and the concentration was measured at a flow rate of 1 ml/min and a temperature of 40 ℃. Polystyrene was used as a standard sample, and the weight average molecular weight was calculated by comparative conversion. The detector used was a differential refractometer.

< method for producing Polyrotaxane (A) to be used >

Production example (RX-1 production)

(1-1) preparation of PEG-COOH:

as a polymer for forming an axial molecule, linear polyethylene glycol (PEG) having a molecular weight of 10,000 was prepared.

The following recipe was prepared:

PEG 10g

TEMPO (2,2,6, 6-tetramethyl-1-piperidinyloxy free radical) 100mg

1g of sodium bromide is added into the mixture,

the ingredients were dissolved in 100mL of water. To this solution, 5mL of a commercially available aqueous sodium hypochlorite solution (5% effective chlorine concentration) was added, and the mixture was stirred at room temperature for 10 minutes. Then, ethanol was added in a range of 5mL at maximum to terminate the reaction. Then, the mixture was extracted with 50mL of dichloromethane, then the dichloromethane was distilled off, dissolved in 250mL of ethanol, and then reprecipitated at-4 ℃ for 12 hours, PEG-COOH was recovered, and dried.

(1-2) preparation of polyrotaxane:

the above-mentioned system is3g of PEG-COOH and 12g of alpha-cyclodextrin (alpha-CD) were dissolved in 50mL of warm water at 70 ℃ respectively, and the resulting solutions were mixed and mixed by shaking thoroughly. Then, the mixed solution was reprecipitated at 4 ℃ for 12 hours, and the precipitated inclusion complex was recovered by freeze-drying. Then, 0.13g of amantadine was dissolved in 50ml of Dimethylformamide (DMF) at room temperature, and then the inclusion complex was added thereto, followed by rapid and thorough mixing with shaking. Next, BOP reagent (benzotriazol-1-yl-oxy-tris (dimethylamino) phosphonium) dissolved in DMF was further added

Hexafluorophosphate) 0.38g, and mixed well with shaking. Further, 0.14ml of diisopropylethylamine dissolved in DMF was added thereto, and the mixture was thoroughly shaken and mixed to obtain a slurry-like reagent.

The slurry-like reagent obtained above was allowed to stand at 4 ℃ for 12 hours. Then, 50ml of a DMF/methanol mixed solvent (volume ratio: 1/1) was added thereto, and the mixture was mixed and centrifuged to remove the supernatant. Further, the precipitate was obtained by washing with the DMF/methanol mixed solution, then washing with methanol, and centrifugal separation. The obtained precipitate was dried under vacuum, dissolved in 50mL of dimethyl sulfoxide (DMSO), and the obtained transparent solution was dropped into 700mL of water to precipitate polyrotaxane. The precipitated polyrotaxane was recovered by centrifugation and dried in vacuum. Further, the resulting polymer was dissolved in DMSO, precipitated in water, recovered and dried to obtain a purified polyrotaxane. The amount of α -CD included in this case was 0.25.

Wherein the inclusion amount is determined by adding deuterated dimethyl sulfoxide (DMSO-d)₆) Dissolving polyrotaxane by¹The measurement was carried out by an H-NMR measuring apparatus (JNM-LA 500 manufactured by Japan electronic Co., Ltd.) by the following method.

Wherein X, Y and X/(Y-X) have the following meanings.

X: an integral value of protons derived from hydroxyl groups of 4 to 6ppm of cyclodextrin

Y: an integral value of protons derived from methylene chains of cyclodextrin and PEG of 3 to 4ppm

X/(Y-X): proton ratio of cyclodextrin to PEG

First, X/(Y-X) when the theoretical maximum amount of inclusion is 1 is calculated in advance, and this value is compared with X/(Y-X) calculated from the analysis value of the actual compound, thereby calculating the amount of inclusion.

(1-3) introduction of side chain to polyrotaxane:

500mg of the purified polyrotaxane was dissolved in 50mL of a 1mol/L NaOH aqueous solution, 3.83g (66mmol) of propylene oxide was added, and the mixture was stirred at room temperature for 12 hours under an argon atmosphere. Then, the polyrotaxane solution is neutralized with 1mol/L HCl aqueous solution until the pH value is 7-8, dialyzed by a dialysis tube, and then freeze-dried to obtain the hydroxypropylated polyrotaxane. Using the obtained hydroxypropylated polyrotaxane¹H-NMR and GPC confirmed that the compound was a hydroxypropylated polyrotaxane having a desired structure.

The modification degree of hydroxypropyl group to OH group of cyclic molecule was 0.5, and the weight average molecular weight Mw measured by GPC was 50,000.

5g of the obtained hydroxypropylated polyrotaxane was dissolved in 15g of epsilon-caprolactone at 80 ℃ to prepare a mixture. After stirring the mixture at 110 ℃ for 1 hour while flowing dry nitrogen, 0.16g of a50 wt% xylene solution of tin (II) 2-ethylhexanoate was added and the mixture was stirred at 130 ℃ for 6 hours. Then, xylene was added to obtain a polycaprolactone-modified polyrotaxane xylene solution into which a side chain having a nonvolatile concentration of about 35% by mass was introduced.

(1-4) preparation of a side chain-modified polyrotaxane into which an OH group is introduced (RX-1: corresponding to polyrotaxane (A) used in the present invention);

the polycaprolactone-modified polyrotaxane xylene solution prepared as described above was dropped in hexane, recovered, and dried, whereby a side chain-modified polyrotaxane (RX-1) having an OH group as the terminal of the side chain was obtained.

The polyrotaxane (A): the physical properties of RX-1 are as follows.

Weight average molecular weight of polyrotaxane Mw (GPC): 200,000.

Degree of modification of side chain: 0.5 (50% when expressed as%).

Molecular weight of side chain: averaging about 350.

Polyrotaxane (A) having a hydroxyl group at the end of the side chain.

< production of RX-2 >

RX-2 was obtained in the same manner as for RX-1, except that 30g of ε -caprolactone was used. The physical properties of this polyrotaxane (RX-2) are shown below.

Degree of modification of side chain: 0.5 (50%).

Molecular weight of side chain: averaging about 650.

Weight average molecular weight of polyrotaxane Mw (GPC): 350000.

polyrotaxane (A) having a hydroxyl group at the end of the side chain.

< production of RX-3 >

RX-3 was obtained in the same manner as in RX-1 except that linear polyethylene glycol (PEG) having a molecular weight of 20000 was used as the polymer for forming axial molecules and epsilon-caprolactone was changed to 20 g. The physical properties of this polyrotaxane (RX-3) are shown below.

Degree of modification of side chain: 0.5 (50%).

Molecular weight of side chain: averaging about 450.

Weight average molecular weight of polyrotaxane Mw (GPC): 300000.

polyrotaxane (A) having a hydroxyl group at the end of the side chain.

< polyiso (thio) cyanate Compound (B) >

XDI: m-xylylene diisocyanate.

< urethane prepolymer (B2) >

Urethane prepolymer (B2) shown in table 1 below was prepared.

[ Table 1]

The content (molar mass concentration (mol/kg)) of iso (thio) cyanate present in the prepolymer

(U) is the content (molar mass concentration (mol/kg)) of urethane bond existing in the prepolymer

< production example of urethane prepolymer (B2) >

Production example Pre-1

In a flask equipped with a nitrogen inlet tube, a thermometer and a stirrer, 50g of 2, 4-tolylene diisocyanate, 32g of polyoxytetramethylene glycol (number average molecular weight: 1000) and 10g of 1, 4-butanediol were reacted at 80 ℃ for 8 hours under a nitrogen atmosphere to obtain an isocyanate-terminated urethane prepolymer having an iso (thio) cyanate equivalent of 319 (to obtain Pre-1).

Production example Pre-2 production example

In a flask equipped with a nitrogen inlet, a thermometer and a stirrer, 1000g of 2, 4-tolylene diisocyanate and 1800g of polyoxytetramethylene glycol (number average molecular weight: 1000) were reacted at 70 ℃ for 4 hours under a nitrogen atmosphere. Then, 240g of diethylene glycol was added and the reaction was carried out at 70 ℃ for 4 hours to obtain an isocyanate terminated urethane prepolymer having an iso (thio) cyanate equivalent of 905 (to obtain Pre-2).

Production example Pre-3

A urethane prepolymer having isocyanate groups at the ends and having an iso (thio) cyanate equivalent of 539 was obtained in the same manner as in production example Pre-2 except that 130g of diethylene glycol was used (to obtain Pre-3).

Production example Pre-4

An isocyanate-terminated urethane prepolymer having an iso (thio) cyanate equivalent of 1500 (obtained as Pre-4) was obtained in the same manner as in preparation example Pre-2, except that 2300g of polyoxytetramethylene glycol (number average molecular weight: 1000) was used.

Production example Pre-5

A urethane prepolymer having an isocyanate group at the end and having an isocyanate equivalent of 338 (obtained as Pre-5) was obtained in the same manner as in preparation example Pre-2, except that 1500g of polyoxytetramethylene glycol (number average molecular weight: 1000) and 50g of diethylene glycol were used.

Production example Pre-6

A urethane prepolymer having isocyanate groups at the ends and having an isocyanate equivalent of 4580 (obtained by Pre-6) was obtained in the same manner as in preparation example Pre-2, except that 2500g of polyoxytetramethylene glycol (number average molecular weight: 1000) and 300g of diethylene glycol were used.

< active Hydrogen-containing Compound (C) having an active Hydrogen group other than polyrotaxane (A) >

PL 1: デュラノ - ル (polycarbonate diol, number average molecular weight 500) manufactured by Asahi Kasei Chemicals K.K

BudioH: 1, 4-butanediol

TMP: trimethylolpropane

TMP-30: trimethylolpropane Tripolyoxyethylene ether manufactured by Nippon emulsifier Co., Ltd

And (3) PEMP: pentaerythritol tetrakis (3-mercaptopropionate)

MOCA: 4,4' -methylenebis (o-chloroaniline)

TMGdiAB: trimethylene glycol-di-p-aminobenzoate

PPG 7: average molecular weight of polypropylene glycol type 700

< other ingredients >

CeO₂: cerium oxide (cerium oxide powder having an average particle diameter of 0.2 μm).

L5617: モメンティブ Silicone foam stabilizer

SZ 1142: silicone foam stabilizer manufactured by Dongli-Dow Corning Co., Ltd

ET: TOYOCAT-ET (Tosoh corporation)

920-40: microcapsule 920-40 (manufactured by Japan フィライト Co., Ltd.)

< example 1>

RX-1(100 parts by mass) of component (A) was dissolved at 40 ℃ in a flask equipped with a nitrogen inlet tube, a thermometer and a stirrer under a nitrogen atmosphere according to the following formulation, and was stirred and mixed with XDI (15 parts by mass) of component (B) to prepare a uniform solution, thereby obtaining a polymerizable composition. The amounts of each component are shown in Table 2. The molar ratio of the total number of moles of active hydrogen-containing groups (total number of moles of OH groups in the side chain of the polyrotaxane (A) RX-1) to the isocyanate group(s) in the component XDI (B) is shown. The molar ratio of the total active hydrogen group-containing moles (total number of moles of OH groups in the side chain of the polyrotaxane (A) RX-1 and total number of moles of OH groups in the cyclodextrin ring of RX-1) to the isocyanate groups in the XDI (S) in the component (B) is shown.

Prescription:

(A) the method comprises the following steps RX-1100 parts by mass.

(B) The method comprises the following steps XDI 15 parts by mass.

The polymerizable composition was poured into a flat mold. Subsequently, the cured product was cured at 80 ℃ for 2 hours and then at 90 ℃ for 4 hours. After the polymerization is completed, the urethane resin is taken out of the mold. The obtained urethane resin had an abrasion resistance of 3.9 and a D hardness of 30. The wear resistance and hardness were evaluated as follows. The results are shown in Table 3.

[ evaluation items ]

(1) Wear resistance: a single-side polisher of ECOMET-3 manufactured by BUEHLER was used as a polisher, and the abrasion resistance was evaluated by polishing with a polishing paper (#600) while running water under a load of 7 lbs., at a rotation speed of 200rpm, for a polishing time of 5 minutes. The following methods were adopted as evaluation methods.

(abrasion amount by polishing/weight of resin before polishing) × 100 (%)

(2) The Shore D hardness was measured by a durometer manufactured by Nippon Polymer Meter according to JIS standard (hardness test) K6253.

< example 2>

RX-1(100 parts by mass) of component (A), PL1(100 parts by mass) of component (C), TMP (30 parts by mass), and TMP-30(100 parts by mass) were stirred and mixed at 40 ℃ under a nitrogen flow in a flask equipped with a nitrogen inlet tube, a thermometer, and a stirrer to prepare a uniform solution, which was then returned to room temperature, XDI (220 parts by mass) of component (B) was added thereto, and the mixture was stirred uniformly to obtain a polymerizable composition. The amounts of each component are shown in Table 2. The molar ratio of the total number of active hydrogen-containing groups to the isocyanate groups of component XDI (B) is shown. The molar ratio of the total active hydrogen-containing groups to the isocyanate groups of component (B), XDI, is shown. Including the total number of moles of active hydrogen-containing groups, the number of moles of all active hydrogen-containing groups, and the number of moles of active hydrogen-containing groups of component (C).

(A) The method comprises the following steps RX-1100 parts by mass.

(B) The method comprises the following steps XDI 220 parts by mass.

(C) The method comprises the following steps PL 1100 parts by mass, TMP 30 parts by mass and TMP-30100 parts by mass.

The polymerizable composition was poured into a flat mold. Subsequently, the cured product was cured at 80 ℃ for 2 hours and then at 90 ℃ for 4 hours. After the polymerization is completed, the urethane resin is taken out of the mold. The obtained urethane resin had an abrasion resistance of 2.9% and a D hardness of 64. The results are shown in Table 3.

< examples 3 to 7, comparative examples 1 and 2>

Cured products were produced and evaluated in the same manner as in example 2, except that the polymerizable compositions having the compositions shown in Table 2 were used. The results are shown in Table 3.

< example 8>

Cured products were produced and evaluated in the same manner as in example 1, except that the polymerizable compositions having the compositions shown in Table 2 were used. The results are shown in Table 3.

< example 9>

In a flask equipped with a nitrogen inlet tube, a thermometer and a stirrer, Pre-1(463 parts by mass) as component (B2) and dry cerium oxide powder (30 parts by mass) having an average particle size of 0.2 μm were introduced under a nitrogen stream and sufficiently stirred. Then, RX-1(100 parts by mass) of separately prepared component (A), PL1(100 parts by mass) of component (C), and BudioH (42 parts by mass) were stirred and mixed at a temperature of 60 ℃ to prepare a homogeneous solution, which was introduced into the flask. Then, the flask was further stirred and mixed to obtain a polymerizable composition. The amounts of each component are shown in Table 2. The molar ratio of the total number of active hydrogen-containing groups to the isocyanate groups of component XDI (B) is shown. The molar ratio of the total active hydrogen-containing groups to the isocyanate groups of component (B), XDI, is shown. Including the total number of moles of active hydrogen-containing groups, the number of moles of all active hydrogen-containing groups, and the number of moles of active hydrogen-containing groups of component (C).

(A) The method comprises the following steps RX-1100 parts by mass

(B) The method comprises the following steps Pre-1463 parts by mass

(C) The method comprises the following steps PL 1100 parts by mass and BudiOH 42 parts by mass

(other ingredients): CeO (CeO)₂30 parts by mass.

The polymerizable composition was poured into a flat mold. Next, the cured product was cured at 80 ℃ for 2 hours and then at 90 ℃ for 4 hours. After the polymerization is completed, the urethane resin is taken out of the mold. The obtained urethane resin had an abrasion resistance of 2.2% and a D hardness of 65. The results are shown in Table 3.

[ Table 2]

TABLE 2

[ Table 3]

No.	Abrasion resistance (%)	D hardness
			Example 1	3.9	30
Example 2	2.9	64
			Example 3	2.2	60
Example 4	4.8	64
			Example 5	4.4	69
Example 6	1.9	58
			Example 7	1.1	63
Example 8	2.5	40
			Example 9	2.2	65
Comparative example 1	10.0	63
			Comparative example 2	6.0	70

< example 10>

RX-1(100 parts by mass) of component (A) and MOCA (21 parts by mass) of component (C) were mixed at 120 ℃ to prepare a uniform solution, which was then thoroughly degassed and cooled to 100 ℃. To the homogeneous solution was added Pre-2(296 parts by mass; urethane prepolymer (B2)) of component (B) heated to 70 ℃ and the mixture was stirred by a rotary and rotary stirrer to obtain a homogeneous polymerizable composition. The amounts of each component are shown in Table 4. The molar ratio of the total number of active hydrogen-containing groups to the isocyanate group(s) in the component (B), Pre-2, is shown in Table 4. The molar ratio of the total active hydrogen-containing groups to the isocyanate (thio) groups in the component (B), Pre-2, is also shown in Table 4. Is a value including the total number of moles of active hydrogen-containing groups, the number of moles of all active hydrogen-containing groups, and the number of moles of active hydrogen-containing groups of component (C).

(A) The method comprises the following steps RX-1100 parts by mass.

(B) The method comprises the following steps Pre-2296 parts by mass.

(C) The method comprises the following steps MOCA 21 parts by mass.

The polymerizable composition was injected into a mold and cured at 100 ℃. After completion of the polymerization, the urethane resin was taken out from the mold to obtain a urethane resin having a thickness of 2 mm. The resulting urethane resin had a polishing rate of 1.9 μm/hr, a scratch resistance of 1, a Taber abrasion amount of 19mg, a D hardness of 30 and a density of 1.1g/cm³The hysteresis loss was 10%. The results are shown in Table 5. The wear resistance and hardness were evaluated as follows.

[ evaluation items ]

(3) Polishing rate: the polishing conditions are as follows.

Polishing the pad: 380 phi.

The polished object: a 2 inch sapphire wafer 3 piece.

Slurry preparation: FUJIMI COMPOL-80 stock solution.

Pressure: 411g/cm²。

The number of rotations: 60 rpm.

Time: for 1 hour.

Under the above conditions, the polishing rate at the time of polishing was measured.

(4) Scratch (mar): it was confirmed that the wafer was scratched or not when polished under the conditions described in (3) above. The evaluation was carried out according to the following criteria.

1: no scratches were found both visually and with a laser microscope.

2: the scratch was not confirmed by visual observation, but the presence of the scratch was confirmed by a laser microscope.

3: by visual inspection, 1 to 2 scratches were observed only at the edge of the wafer.

4: by visual observation, 3 or more scratches can be observed only at the edge of the wafer, or 1 to 2 scratches can be observed over the entire wafer.

5: by visual observation, 3 or more scratches were observed over the entire wafer.

(5) Taber abrasion loss: the measurement was carried out by means of a 5130 model manufactured by Taber. The Taber abrasion test was carried out under a load of 1Kg, a rotation speed of 60rpm, a rotation number of 1000 revolutions, and an abrasion wheel of H-18.

(6) Density: the density was measured by using DSG-1 manufactured by Toyo Seiki Seisaku-Sho Ltd.

(7) Hysteresis loss: a resin punched out into a dumbbell No. 8 having a thickness of 2mm was stretched at a rate of 10 mm/min for 20mm by Autograph of AG-SX manufactured by Shimadzu corporation, and then the hysteresis loss at the time when the stress was returned to 0 was measured.

Examples 11 to 14 and comparative example 3

Cured products were produced and evaluated in the same manner as in example 10, except that the polymerizable compositions having the compositions shown in Table 4 were used. The results are shown in Table 5.

[ Table 4]

TABLE 4

[ Table 5]

TABLE 5

< example 15>

To Pre-2(296 parts by mass; urethane prepolymer (B2)) of component (B) heated to 70 ℃ was added L5617(6.3 parts by mass) of the other component, and the mixture was vigorously stirred at 2000rpm in a nitrogen atmosphere using a stirrer with a stirring blade as a whipper, and air bubbles were taken in by the Mechanical Floss method. RX-1(100 parts by mass) of component (A) and MOCA (21 parts by mass) of component (C) were mixed to prepare a homogeneous solution at 120 ℃. After sufficient deaeration, the homogeneous solution cooled to 100 ℃ was added to Pre-2 having the above-mentioned cells taken therein, and stirred vigorously at 2000rpm under a nitrogen atmosphere using a stirrer having a paddle as a whipper, whereby cells were taken in by the Mechanical flow method to obtain a homogeneous polymerizable composition having a foam structure. The amounts of each component are shown in Table 6. The molar ratio of the total number of active hydrogen-containing groups to the isocyanate group(s) in the component (B), Pre-2, is shown in Table 6. The molar ratio of the total active hydrogen-containing groups to the isocyanate (thio) groups in the component (B), Pre-2, is also shown in Table 6. Is a value including the total number of moles of active hydrogen-containing groups, the number of moles of all active hydrogen-containing groups, and the number of moles of active hydrogen-containing groups of component (C).

(A) The method comprises the following steps RX-1100 parts by mass.

(B) The method comprises the following steps Pre-2296 parts by mass.

(C) The method comprises the following steps MOCA 21 parts by mass.

(other ingredients): l-56176.3 parts by mass.

The polymerizable composition was injected into a mold and cured at 100 ℃. After completion of the polymerization, the urethane resin was taken out from the mold to obtain a foamed urethane resin having a thickness of 2 mm. The resulting urethane resin had a polishing rate of 3.2 μm/hr, a scratch resistance of 1, a Taber abrasion amount of 15mg, a D hardness of 20, and a density of 0.7g/cm³The hysteresis loss was 10%. These evaluations were carried out in the same manner as in example 10. The results are shown in Table 7.

< examples 16 to 20 and comparative example 4>

Cured products were produced and evaluated in the same manner as in example 15, except that the polymerizable compositions having the compositions shown in Table 6 were used. The results are shown in Table 7.

< example 21>

To Pre-2(341 parts by mass; urethane prepolymer (B2)) of component (B) heated to 70 ℃ were added SZ1142(6.8 parts by mass), water (0.4 part by mass) and ET (0.2 part by mass) as other components, and the mixture was stirred at 2000rpm for 1 minute using a rotary-rotary stirrer (シンキー). RX-1(100 parts by mass) of component (A) and MOCA (21 parts by mass) of component (C) were mixed together to prepare a homogeneous solution at 120 ℃. After sufficient degassing, the uniform solution cooled to 100 ℃ was added to Pre-2 having the above-mentioned bubbles taken therein, and stirred at 2000rpm for 1 minute using a revolution and rotation stirrer (manufactured by シンキー Co.) to obtain a uniform polymerizable composition having a foam structure. The amounts of each component are shown in Table 6. The molar ratio of the total number of active hydrogen-containing groups to the isocyanate group(s) in the component (B), Pre-2, is shown in Table 6. The molar ratio of the total active hydrogen-containing groups to the isocyanate (thio) groups in the component (B), Pre-2, is also shown in Table 6. Is a value including the total number of moles of active hydrogen-containing groups, the number of moles of all active hydrogen-containing groups, and the number of moles of active hydrogen-containing groups of component (C).

(A) The method comprises the following steps RX-1100 parts by mass

(B) The method comprises the following steps Pre-2341 parts by mass

(C) The method comprises the following steps MOCA 21 parts by mass

(other ingredients): SZ 11426.8 parts by mass, 0.4 part by mass of water and ET 0.2 part by mass.

The polymerizable composition was injected into a mold and cured at 100 ℃. After completion of the polymerization, the urethane resin was taken out from the mold to obtain a foamed urethane resin having a thickness of 2 mm. The resulting urethane resin had a polishing rate of 3.4 μm/hr, a scratch resistance of 1, a Taber abrasion amount of 14mg, a D hardness of 23, and a density of 0.9g/cm³The hysteresis loss was 8%. These evaluations were carried out in the same manner as in example 10. The results are shown in Table 7.

< example 22>

Cured products were produced and evaluated in the same manner as in example 21, except that the polymerizable compositions having the compositions shown in Table 6 were used. The results are shown in Table 7.

< example 23>

920-40(3.4 parts by mass) was added to Pre-2(307 parts by mass; urethane prepolymer (B2)) of component (B) heated to 70 ℃ and the mixture was stirred at 2000rpm for 1.5 minutes using a rotary and rotary stirrer (manufactured by シンキー). RX-1(100 parts by mass) of component (A) and MOCA (21 parts by mass) of component (C) were mixed to prepare a homogeneous solution at 120 ℃. After sufficient degassing, the uniform solution cooled to 100 ℃ was added to Pre-2 having the above-mentioned bubbles taken therein, and stirred at 2000rpm for 1.5 minutes using a revolution and rotation stirrer (manufactured by シンキー), whereby a uniform polymerizable composition having a foam structure was obtained. The amounts of each component are shown in Table 6. The molar ratio of the total number of active hydrogen-containing groups to the isocyanate group(s) in the component (B), Pre-2, is shown in Table 6. The molar ratio of the total active hydrogen-containing groups to the isocyanate (thio) groups in the component (B), Pre-2, is also shown in Table 6. Is a value including the total number of moles of active hydrogen-containing groups, the number of moles of all active hydrogen-containing groups, and the number of moles of active hydrogen-containing groups of component (C).

(A) The method comprises the following steps RX-1100 parts by mass

(B) The method comprises the following steps Pre-2307 parts by mass

(C) The method comprises the following steps MOCA 21 parts by mass

(other ingredients): 920 to 403.4 parts by mass

The polymerizable composition was injected into a mold and cured at 100 ℃. After completion of the polymerization, the urethane resin was taken out from the mold to obtain a foamed urethane resin having a thickness of 2 mm. The resulting urethane resin had a polishing rate of 3.3 μm/hr, a scratch resistance of 1, a Taber abrasion amount of 17mg, a D hardness of 27, and a density of 0.8g/cm³The hysteresis loss was 25%. These evaluations were carried out in the same manner as in example 10. The results are shown in Table 7.

< example 24>

Cured products were produced and evaluated in the same manner as in example 22, except that polymerizable compositions having the compositions shown in table 6 were used. The results are shown in Table 7.

[ Table 6]

TABLE 6

[ Table 7]

TABLE 7

As is clear from the above examples and comparative examples, the urethane resin for polishing obtained by using the polyrotaxane of the component (a) has excellent durability.

Description of the symbols

1: polyrotaxane

2: axial molecules

3: cyclic molecules

4: bulky terminal groups

5: side chains

Claims (6)

1. A polymerizable composition for producing a foamed urethane resin, which comprises the following components:

a polyrotaxane (A) having a complex molecular structure formed of an axis molecule and a plurality of cyclic molecules including the axis molecule and having an active hydrogen group-containing side chain introduced into at least a part of the cyclic molecules, and

polyiso (thio) cyanate compound (B),

the polyisocyanate compound (B) is contained in an amount of 3 to 2000 parts by mass based on 100 parts by mass of the polyrotaxane (A),

the polyiso (thio) cyanate compound (B) used was: a urethane prepolymer (B2) having an isocyanate (thio) group at the molecular end, which is obtained by reacting a 2-functional active hydrogen-containing compound (C1) having 2 active hydrogen-containing groups in the molecule with a 2-functional isocyanate (thio) group-containing compound (B1) having 2 isocyanate (thio) groups in the molecule, and

the polyiso (thio) cyanate compound (B) containing the urethane prepolymer (B2) has an iso (thio) cyanate equivalent weight in the range of 300 to 5000.

2. The polymerizable composition according to claim 1, further comprising an active hydrogen-containing compound (C) having an active hydrogen-containing group other than the polyrotaxane (A).

3. The polymerizable composition according to claim 2, wherein the active hydrogen-containing compound (C) contains an amino Compound (CA) having an amino group as the active hydrogen-containing group.

4. The polymerizable composition according to claim 2 or 3, which comprises, per 100 parts by mass of the polyrotaxane (A):

10 to 2000 parts by mass of the polyiso (thio) cyanate compound (B), and

3 to 2000 parts by mass of the active hydrogen-containing compound (C).

5. A polishing pad comprising a foamed urethane resin produced from the polymerizable composition according to any one of claims 1 to 4.

6. A foamed urethane resin produced from the polymerizable composition according to any one of claims 1 to 4.

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